Synthetic alkali metal aluminosilicates and use in paints

ABSTRACT

A family of novel and unique synthetic alkali metal alumino-silicates (SAMS) are produced by the hydrothermal reaction between kaolin and alkali metal silicates. The integrated composition of the SAMS products is a unique entity having an overall composition of 
     
         xM.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :z H.sub.2 O 
    
     where x is the number of moles of alkali metal oxide and is an integer from 0.01 to 2.0, M is the alkali metal, y is the number of moles of SiO 2  in the unique SAMS compositions and is an integer greater than 2.0, and z is the number of moles of bound water and is an integer ranging form 1.0 to 5.0. the unique SAMS compositions are structured materials in which the structure can be controlled, and are therefore useful as functional fillers, as TiO 2  extenders, as silica extenders or as reinforcing agents for paper, paint, rubber, plastics and specialty products.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of Ser. No. 07/297,738, now U.S. Pat. No.5,035,873, filed Jan. 17, 1989, which is a continuation of Ser. No.06/875,120 filed June 17, 1986; said Ser. No. 07/297,738, now U.S. Pat.No. 5,075,873 being a continuation-in-part of Ser. No. 07/116,805, filedNov. 3, 1987, now U.S. Pat. No. 4,812,299, and related to:

Ser. No. 07/298,720, filed Jan. 19, 1989, now U.S. Pat. No. 4,933,387;

Ser. No. 07/298,721, filed Jan. 19, 1989, now U.S. Pat. No. 4,863,796;

Ser. No. 07/298,719, filed Jan. 19, 1989, now U.S. Pat. No. 4,968,728;

Ser. No. 07/298,722, filed Jan. 19, 1989, now abandoned;

Ser. No. 07/298,718, filed Jan. 19, 1989, now U.S. Pat. No. 4,879,323;

Ser. No. 07/299,279, filed Jan. 19, 1989; now U.S. Pat. No. 4,954,468

Ser. No. 07/299,194, filed Jan. 19, 1989, now U.S. Pat. No. 4,902,729;

Ser. No. 07/299,278, filed Jan. 19, 1989, now U.S. Pat. No. 4,902,657;

all of said Ser. Nos. 07/298,720, 07/298,721, 07/298,719, 07/298,722,07,298,718, 07,299,279, 07/299,194 and 07/299,278 being divisionalapplications of Ser. No. 07/166,805.

FIELD OF THE INVENTION

This invention relates to novel and unique synthetic alkali metalalumino-silicates (SAMS) compositions and, more particularly, tosynthetic alkali metal alumino-silicates produced by the hydrothermalreaction of kaolin clays and alkali metal silicates. The preferredmethod entails the hydrothermal treatment of an aqueous dispersion of aclay pigment with an alkali metal silicate at molar ratios of alkalimetal silicate base (B) to clay (C) of less than 1.0, but SAMScompositions and mixtures of SAMS and zeolites can be formed at B/Cratios greater than 1.0. The SAMS compositions have specific advantagesas reinforcing extenders or functional fillers for paper, paints, rubberand polymer systems and an opacifying agent for paper among its manyuses.

BACKGROUND OF THE INVENTION

Alkali metal silicate materials, such as sodium alumino-silicates, arewell known. Broadly speaking, there are two kinds of alkali metalalumino-silicate materials known in the prior art-the natural and thesynthetic alkali metal alumino-silicates.

The alkali metal alumino-silicates known as natural zeolites are minedproducts which are crystalline in nature. Synthetic alkali metalalumino-silicate products are either amorphous or crystalline reactionproducts. The crystalline synthetic alkali metal alumino-silicates arealso called synthetic zeolites. Various types of amorphous syntheticalkali metal alumino-silicates are known as well as synthetic silicasand alumino-silicates.

In order to fully appreciate the present invention it is necessary todraw the appropriate distinctions between the unique compositions of thepresent invention and the prior art compositions of specific silicas andsynthetic silicates referred to in general above.

ZEOLITES

The prior art description of the nature of zeolites can be found in theU.S. Pat. No. 3,702,886 and is incorporated herein by reference.

Both natural and synthetic zeolites can be broadly classified ascrystalline alkali/alkaline earth metal alumino-silicates having uniqueproperties. Synthetic zeolites are ordered, porous crystallinealumino-silicates having a definite crystalline structure within whichthere are a large number of small cavities which are interconnected by anumber of still smaller channels. The cavities and channels areprecisely uniform in size. Since the dimensions of these pores are suchas to accept for adsorption molecules of certain dimensions whilerejecting those of larger dimensions, these materials have come to beknown as "molecular sieves" and are utilized in a variety of ways totake advantage of these properties.

Such molecular sieves include a wide variety of positive ion-containingcrystalline alumino-silicates, both natural and synthetic. Thesealumino-silicates can be described as a rigid three dimensional networkof SiO₄ and AlO₄ in which the tetrahedra are cross-linked by the sharingof oxygen atoms whereby the ratio of the total aluminum and siliconatoms to oxygen is 1:2. The electrovalence of the tetrahedra-containingaluminum is balanced by the inclusion in the crystal of a cation, forexample, an alkali metal or an alkaline earth metal cation. This can beexpressed by formula wherein the ratio of Al to the number of thevarious cations, such as Ca/2, Sr/2, Na, K, or Li, is equal to unity.One type of cation can be exchanged either in entirety or partially byanother type of cation utilizing ion exchange techniques in aconventional manner. By means of such cation exchange, it has beenpossible to vary the size of the pores in the given alumino-silicate bysuitable selection of the particular cation. The spaces between thetetrahedra are occupied by molecules of water prior to dehydration.

Prior art techniques have resulted in the formation of a great varietyof synthetic crystalline alumino-silicates. These alumino-silicates havecome to be designated by letter or other convenient symbol, asillustrated by zeolite A (U.S. Pat. No. 2,882,243); zeolite X (U.S. Pat.No. 2,882,244); zeolite Y (U.S. Pat. No. 3,130,007); zeolite K-G (U.S.Pat. No. 3,055,654); zeolite ZK-5 (U.S. Pat. No. 3,247,195); zeoliteBeta (U.S. Pat. No. 3,308,069); and zeolite ZK-4 (U.S. Pat. No.3,314,752), merely to name a few.

ZEOLITE IDENTIFICATION

Zeolites A and X may be distinguished from other zeolites and silicateson the basis of their x-ray powder diffraction patterns and certainphysical characteristics. The composition and density are among thecharacteristics which have been found to be important in identifyingthese zeolites.

The basic formula for all crystalline sodium zeolites may be representedas follows:

    Na.sub.2 O:Al.sub.2 O.sub.3 :xSiO.sub.2 :yH.sub.2 O

In general, a particular crystalline zeolite will have values for x andy that fall in a definite range. The value x for a particular zeolitewill vary somewhat since the aluminum atoms and the silicon atoms occupyessentially equivalent positions in the lattice. Minor variations in therelative numbers of these atoms does not significantly alter the crystalstructure or physical properties of the zeolite. For zeolite A, anaverage value for x is about 1.85 with the x value falling within therange 1.85±0.5. For zeolite X, the x value falls within the range2.5±0.5.

The value of y is not necessarily an invariant for all samples ofzeolites. This is true because various exchangeable ions are ofdifferent size, and, since there is no major change in the crystallattice dimensions upon ion exchange, the space available in the poresof the zeolite to accommodate water molecules varies.

The average value for y determined for zeolite A is 5.1. For zeolite Xit is 6.2.

In zeolites synthesized according to the preferred prior art procedure,the ratio of sodium oxide to alumina should equal one. But if all theexcess sodium present in the mother liquor is not washed out of theprecipitated product, analysis may show a ratio greater than one, and ifthe washing is carried too far, some sodium may be ion exchanged byhydrogen, and the ratio will drop below one. It has been found that dueto the ease with which hydrogen exchange takes place, the ratio ofzeolite A lies in the range of ##EQU1## The ratio of zeolite X lies inthe range of ##EQU2## Thus the formula for zeolite A may be written asfollows:

    1.0±0.2Na.sub.2 O:Al.sub.2 O.sub.3 :1.85±0.5SiO.sub.2 :yH.sub.2 O

Thus the formula for zeolite X may be written as follows:

    0.9±0.2Na.sub.2 O:Al.sub.2 O.sub.3 :2.5±0.5SiO.sub.2 :yH.sub.2 O

y may be any value up to 6 for zeolite A and any value up to 8 forzeolite X.

The pores of zeolites normally contain water. The above formulasrepresent the chemical analysis of zeolites A and X. When othermaterials as well as water are in the pores, chemical analysis will showa lower value of y and the presence of other adsorbates. The presence inthe crystal lattice of materials volatile at temperatures below about600 degrees Celsius does not significantly alter the usefulness of thezeolite as an adsorbent since the pores are usually freed of suchmaterials during activation.

PRIOR ART PATENTS

Synthetic alkali metal silicates, such as sodium alumino-silicates, aregenerally produced by the reaction of alum with alkali metal silicates.The resulting product usually has a silica to alumina molar ratio ofabout 11. Amorphous products of this type are known. For example,amorphous products of this type are sold by the J. M. Huber Corporationunder the trademark ZEOLEX®. Specific examples of these products, aswell as methods of their preparation are disclosed in U.S. Pat. Nos.2,739,073; 2,843,346 and 3,582,379.

None of these patents teach or even suggest the synthesis of the uniquecompositions of the present invention by the hydrothermal reactionbetween alkali metal silicate bases and clay at preferred molar ratiosof silicate base to clay of less than 1.0.

Synthetic silicas are also known which are produced by the reaction ofsodium silicates and sulfuric acid at temperatures of about 80 degreesC. The products usually have fixed molar ratios. Various products ofthis type are known in U.S. patents of Satish K. Wason under U.S. Pat.Nos. 3,893,840; 4,067,746; 4,122,160 and 4,422,880. Products of thistype are sold by J. M. Huber Corporation under the ZEO®, ZEOSYL®,ZEOFREE® and ZEODENT® trademarks.

None of the above mentioned patents teach or even suggest the synthesisof the unique compositions of the present invention by the hydrothermalreaction between alkali metal silicate base (B) and clay (c) atpreferred molar ratios of B/C or silicate base to clay of less than 1.0.A comparison of the Fourier Transform Infrared (FT-IR) spectra of anamorphous synthetic silicate (Zeolex 23), an amorphous silica (Hi-Sil233) and a synthetic alkali metal alumino-silicate (SAMS) of the instantinvention is shown in FIG. 1.

Various zeolite products are also known which are produced syntheticallyby the reaction of sodium aluminate and sodium silicates at temperaturesof less than 100 degrees C. This reaction, in general, proceeds to forman intermediate gel or amorphous material which then crystallizes.Zeolites of this type are sold commercially under the designations,zeolite A, zeolite X, zeolite Y, as well as others. These zeolites finduse as absorbents, ion exchange agents, in catalysis and in other areas.A detailed discussion of this art is provided in U.S. Pat. Nos.4,443,422 and 4,416,805 and is hereby incorporated herein by reference.

None of these patents teach or remotely suggest the synthesis of theunique compositions of the present invention by the hydrothermalreaction between alkali metal silicate base (B) and clay (C) atpreferred molar ratios of B/C, or silicate base to clay, of less than1.0. A comparison of the infrared spectra (FT-IR) of zeolites A, X, andY with a synthetic alkali metal alumino-silicate (SAMS) prepared by themethod described in the instant invention is shown in FIG. 2.

The reaction of sodium silicate with kaolin clays has been studied undervarious hydrothermal conditions, as reported by Kurbus, et al, Z. Anorg.Allg. Chem., 1974, Volume 429, pages 156-161. These reactions werestudied under hydrothermal conditions using essentially equivalent molarratios of the kaolin and sodium silicate with the reaction being carriedout in an autoclave. The products of the reactions, as identified byx-ray, electron microscope, and infrared methods, showed that sodiumsilicate reacts with kaolin to form an alumino-silica gel or acrystallized zeolite mineral analcime of the formula:

    Na.sub.2 O:Al.sub.2 O.sub.3 :4SiO.sub.2 :2H.sub.2 O.

In the reaction, the kaolin dissolves and alpha-quartz simultaneouslyappears in the product of reaction.

Kurbus reference specifically teaches the synthesis of a prior artcrystalline zeolite mineral called analcime. This reference does noteven remotely suggest the synthesis of the unique compositions of thepresent invention.

For simplicity, the unique compositions of the instant invention aredescribed as x-ray amorphous materials having attenuated kaolin peaks.The materials will be described in greater detail under the summary ofthe invention. An FT-IR comparison of analcime with a SAMS compositionof the present invention is also given in FIG. 2.

Various reactions of kaolin clays with basic reagents have been studied,including reactions with sodium hydroxide, calcium hydroxide, and thelike.

U.S. Pat. Nos. 3,765,825 and 3,769,383 to Hurst, for example, studiedthe high temperature, high pressure reaction of slurries of clay withalkali metal hydroxides, such as sodium hydroxides. In this reaction,the kaolinite was decomposed and transformed into alumino-silicamaterials. None of these patents even remotely suggest about thesynthesis of the unique composition of the present invention by thehydrothermal reaction between an alkali metal silicate and kaolin clayat preferred molar ratios of silicate to clay of less than 1.0.

Various synthetic amorphous sodium alumino-silicate materials have beenproduced, as described in U.S. Pat. No. 4,213,874, by the reaction ofsodium silicate and sodium aluminate. This patent does not teach or evensuggest the synthesis of the unique composition of the present inventionby the hydrothermal reaction between an alkali metal silicate and kaolinclay.

In U.S. Pat. No. 3,264,130, a hydroxide of barium or calcium is reactedwith a siliceous material. This patent does not teach about thehydrothermal reaction between an alkali metal silicate and kaolin clay.

An amorphous precipitated sodium alumino-silicate pigment is produced inU.S. Pat. No. 3,834,921 by the reaction of sodium silicate and aluminumsulfate. The example of U.S. Pat. No. 3,834,921 teaches about thesynthesis of an alumino-silicate pigment of the silica to alumina ratioof about 11.5 The product is produced by reaction of aluminum sulfateand sodium silicate.

None of the above mentioned patents teach or remotely suggest about thesynthesis of the unique compositions of the present invention by thehydrothermal reaction between alkali metal silicate base (B) and clay(C) at preferred molar ratios of silicate base to clay, or B/C, of lessthan 1.0.

In U.S. Pat. No. 4,075,280, zeolite A is produced by the reaction of acalcined clay with sodium hydroxide. This patent teaches about a newprocess for the preparation of well known prior art zeolite A of welldefined x-ray pattern.

Rod-shaped microcrystalline particulates are produced in U.S. Pat. No.3,837,877 by the reaction of the kaolin clay and an alkali metalhydroxide at molar ratios of hydroxide to clay of at least 2:1. Thispatent does not even remotely suggest about the synthesis of uniquecompositions of the instant invention from the hydrothermal reactionbetween an alkali metal silicate and kaolin clay.

In U.S. Pat. No. 3,784,392, a method is described for preparing finelydivided alumino-silicate pigments from kaolin clays by the hydrothermaltreatment of kaolin clay dispersions with an alkaline earth metalhydroxide, usually calcium hydroxide. The reaction is carried out usinga molar ratio of the hydroxide to the kaolin pigment of at least 1:1 attemperatures of 50 to 200 degrees C. under hydrothermal conditions. Theproduct produced is an amorphous alumino-silicate pigment havingincreased brightness and having particular utility in coating paper.This patent does not even remotely suggest a reaction between an alkalimetal silicate and kaolin to produce unique compositions of the presentinvention.

None of the prior art patents teach the synthesis of novel alkali metalalumino-silicate compositions described herein. The products of thepresent invention are unique and their preparation under the disclosedreaction conditions is truly unexpected. For the sake of brevity, thesynthetic alkali metal alumino-silicates of the instant invention arereferred to as SAMS throughout the body of this patent.

A further background concept necessary to fully appreciate the presentinvention is that of "structure." As used herein, in relation to alkalimetal alumino-silicates, the structure concept is as follows:

It is possible to synthesize alkali metal alumino-silicate or SAMSproducts with varying structure levels in analogy to the structuredefinition set forth in U.S. Pat. No. 3,893,840 to S. K. Wason of J. M.Huber Corporation. Since no universally accepted industrial method forparticle size determination of synthetic fillers exists and since it iscommon practice of filler suppliers to perform the rub-out oilabsorption test, ASTM-D.281, on their products, the definition ofstructure is arbitrarily based on the oil absorption values rather thanthe filler particle size. Conforming to the same definition as in usefor silica structure, e.g., S. K. Wason, "Cosmetic Properties andStructure of Fine Particle Synthetic Precipitated Silica," J. Soc.Cosmet. Chem. 29, 497-521 (August 1978), the synthetic alkali metalalumino-silicates or SAMS products are called VHS (very high structure)type when the oil absorption values are above 200 ml/100 g and VLS (verylow structure) type when the oil absorption values are below 75 ml/100g. The classification of the synthetic alkali metal alumino-silicate orSAMS compositions based on "structure" is shown in Table I as it relatesto oil absorption.

                  TABLE I                                                         ______________________________________                                        DEFINITION: SAMS STRUCTURE VERSUS                                             OIL ABSORPTION                                                                                          Oil Absorption                                      Structure Level           (ml/100 g)                                          ______________________________________                                        VHS      (Very High Structure)                                                                          Above 200                                           HS       (High Structure) 175-200                                             MS       (Medium Structure)                                                                             125-175                                             LS       (Low Structure)   75-125                                             VLS      (Very Low Structure)                                                                           Less than 75                                        ______________________________________                                    

The present invention provides novel synthetic alkali metalalumino-silicate or SAMS compositions and methods for their preparationwhich are unique and unexpected in view of the knowledge of the priorart involving the reaction of clays and alkali metal silicates.

SUMMARY OF THE INVENTION

The present invention relates to a novel family of unique syntheticcompositions hereinafter designated as synthetic alkali metalalumino-silicates or "SAMS" or simply SAMS. The products of the instantinvention relate to a novel family of unique synthetic materials whichare shown by transmission electron microscopy (TEM), FourierTransform-Infrared spectroscopy (FT-IR), x-ray diffraction (XRD), andelectron diffraction (ED) to be unique in composition and morphology andwhich characteristically contain as a minor portion partially alteredkaolin particles which give the characteristic peaks for kaolin seen inthe x-ray diffraction patterns of the SAMS compositions, but which alsocontain as the major portion a non-diffracting amorphous ormicrocrystalline reaction product primarily around the edges, but alsoto some extent over the face of the altered kaolin particle asillustrated by TEM FIGS. 18 through 23.

The TEM FIGS. 18 to 23 show the SAMS product to be altered kaolinplatelets having an integrated rimmed area of amorphous, non-diffractingalkali metal silicate-kaolin reaction product. The integratedcomposition of the SAMS product is a unique entity having an overallcomposition of:

    xM.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

where x is the number of moles of alkali metal oxide and M is the alkalimetal, y is the number of moles of SiO₂ in the SAMS composition, and zis the number of moles of bound water.

The unique products are further characterized by XRD as beingessentially amorphous and having attenuated kaolin peaks as illustratedby FIGS. 33, 34, 35 and 36. The SAMS products are also characterized ashaving infrared spectra (IR) which differ from the IR spectra of thestarting clays, zeolites, and both crystalline and amorphous silicas andsilicates. FIG. 1 compares the infrared spectrum of a SAMS compositionwith the spectra of an amorphous synthetic silicate (Zeolex 23) andsilica (Hi-Sil 233), and with calcined clay. FIG. 2, likewise, comparesthe infrared spectrum of a SAMS composition with the spectra of zeolitesA, X, Y, and analcime. In both FIGS. 1 and 2 the infrared spectrum ofthe SAMS composition is considerably different than the spectra of theother materials. In FIGS. 3 and 4, the infrared spectra of the SAMScompositions of Example One and Two are compared with their respectivestarting clays. In both cases, the spectra of the SAMS compositions areconsiderably different from the spectra of the starting clays, eventhough the area in the 800-400 wavenumber region is quite similar forboth clay and SAMS. The major spectral difference is the 1200-875wavenumber region where the SAMS compositions exhibit a broader, lessdetailed Si--O stretching peak (1200-950 cm⁻¹).

For simplicity, the SAMS compositions will be described as beingessentially amorphous rimmed materials but having attenuated XRD kaolinpeaks.

The preferred unique compositions of the present invention are preparedby the hydrothermal reaction of an alkali metal silicate and clay makingsure that the B/C ratio of the batch compositions are less than 1.0, butby no means limited to values less than 1.0, where B represents themoles of alkali metal silicate and C represents the moles of kaolin clayin a batch composition. While the preferred SAMS compositions areproduced at B/C ratios of less than 1.0, unique SAMS products can alsobe produced at B/C ratios substantially greater than 1.0 by adjustingthe batch composition, pressure, temperature, and reaction time of thehydrothermal reaction. This unique batch composition is heated in astirred reactor using a steam pressure of 50 psi to 360 psi andpreferably between 90 to 150 psi for a reaction time of 15 minutes tofour hours and more preferably between 45 minutes to two hours. At theend of the desired reaction period, the reactor is cooled and the uniqueSAMS product is filtered, washed, dried and milled to the desired degreeof fineness. The alkali metal silicate referred to as base in the SAMSreaction has a SiO₂ to alkali metal oxide ratio of 1-4 and preferablybetween 2.0-3.3. When the alkali metal silicate is sodium silicate, thena preferred sodium form of SAMS composition is produced which can beexpressed in terms of mole ratio of the oxides as follows:

    xNa.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

where x is an integer with a value of from 0.01 to 2.0, y is an integerwith a value greater than 2.0, and z is an integer from 0 to 10 andpreferably 0 to 5.0.

While alkali metal silicates and kaolin are the preferred ingredients inthe SAMS reaction, it is to be understood that the equivalent rawmaterials can be substituted. For instance, the raw materialscorresponding to the synthesis of alkali metal silicates such asreactive silica, synthetic silica, active silica, reactive sand andalkali metal hydroxides and oxides or their equivalent, can be used toaccomplish the same end result as the alkali metal silicate described inthe instant invention. In the like manner, kaolin is the preferred rawmaterial but other sources of silica and alumina, such as alumina,sodium aluminate, aluminum hydroxide or other aluminum sources as wellas synthetic silicas, reactive silicas, silicates or other silicasources, or minerals such as bentonite, hectorite, attapulgite,reconstituted clays, sepiolite, saponite, smectites and the like, can beused without deviating from the spirit of the invention.

It is, accordingly, one object of the present invention to provide novelsynthetic alkali metal alumino-silicate (SAMS) products or pigmentswhich are useful as reinforcing agents, reinforcing extenders,functional fillers, and/or opacifiers for paper, paints, plastics, andother specialty products.

A further object of the invention is to provide a method for theproduction of novel synthetic alkali metal alumino-silicate products bythe reaction of clays and alkali metal silicates under hydrothermalconditions using unique batch compositions and controlled reaction time,temperature and pressure conditions.

It is general object of the present invention to produce value addedunique compositions from relatively inexpensive kaolin or relatedminerals.

It is, accordingly, an object of the present invention to producecontrolled structure synthetic alkali metal alumino-silicate productsfrom mined and refined kaolin by a simplified and highly efficientprocess.

Yet another object of the invention is to produce unique kaolin basedcompositions of higher brightness than the starting kaolin products.

Another object of the instant invention is to produce unique novelproducts of significantly higher opacity than the starting kaolin.

Yet another object of the present invention is to provide controlledstructure and high oil absorption products of unique end-use performancefrom the relatively inexpensive raw material sources.

Another, and more particular object, is to provide unique syntheticalkali metal alumino-silicate compositions of performance features equalto or better than calcined clays without having to use the calcinationprocess.

Yet another object is to provide unique SAMS products of unexpected highion exchange properties to compliment the catalytic properties of knownzeolites.

Yet another objective of the instant invention is to provide uniqueactive support material for catalyst applications.

Another objective of the instant invention is to provide unique SAMScompositions of very low abrasion properties when compared with calcinedclays.

Another very important objective of the instant invention is to providesynthetic pigments of superior paper coating properties than calcinedclays.

Another object of the instant invention is to provide unique syntheticproducts which can extend expensive functional fillers, extenders,pigments and value added products such as calcined clays, fumed silicasand silica gels, synthetic silicas, aluminum trihydrate (ATH), titaniumdioxide (TiO₂), synthetic silicates, synthetic calcium silicates andrelated compounds.

Yet another important and particular object of the invention is toprovide unique SAMS compositions of high scattering coefficient andexcellent opacifying properties for use in extending the expensivetitanium dioxide compositions in such end-use applications as paper,paints, rubber and plastic concentrates.

Yet another most important object of the present invention is to providea new SAMS technology base for the conversion of inexpensive rawmaterials to commercially viable value-added functional products.

A still further object of the invention is to provide articles ofmanufacture comprising paper, latex paints, plastics, paint flatting,rubber, dry liquid carrier, defoamers, antiblocking, and other productscontaining, as a reinforcing agent or functional filler or extender, anovel synthetic alkali metal alumino-silicate product produced by thehydrothermal reaction of clays and alkali metal silicates.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In satisfaction of the foregoing objects and advantages, there isprovided by this invention essentially amorphous synthetic alkali metalalumino-silicates (SAMS) which are of the general formula

    xM.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

wherein x is the number of moles of alkali metal oxide, M is the alkalimetal, y is the number of moles of SiO₂, and z is the number of moles ofbound water associated with unique SAMS compositions.

These products may be characterized as substantially amorphous withattenuated kaolin peaks as characterized by the present state of the artXRD, and yet may be considered micro-crystalline at a future date as ourlearning curve in the characterization of SAMS type products increases.The present invention provides unique SAMS products which are shown byTEM to be rimmed amorphous compositions integrated with altered kaolinplatelets. The SAMS products have oil absorption values ranging from 40to above 200 ml/100 g, surface areas ranging from 2 to 300 m² /g, highmonovalent cation exchange capacities of the order of up to 200milliequivalent/100 g and very low abrasion characteristics.

Also provided by the present invention is a method for production ofthese synthetic alkali metal alumino-silicate products which comprisesthe hydrothermal reaction of a slurry of a clay with an alkali metalsilicate wherein the preferred molar ratio of alkali metal silicate base(B) to clay (C) in the starting reaction mixture is less than 1.0,although unique SAMS compositions can be produced at ratios higher than1.0 under preselected reaction conditions.

There is also provided by the present invention compositions comprisingpaper, paints, plastics, rubber, defoamer, and specialty products, whichcontain the novel synthetic alkali metal alumino-silicate materials ofthis invention.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to facilitate the understanding of this invention, referencewill now be made to the appended drawings. The drawings should not beconstrued as limiting the invention but are exemplary only.

FIG. 1 shows a comparison of the FT-IR scans of Zeolex 23, an amorphoussodium alumino-silicate, Hi-Sil 233, an amorphous synthetic silica,Hycal, a calcined kaolin, and the SAMS composition from Example Two

FIG. 2 shows a comparison of the FT-IR scans of zeolites A, X, Y andanalcime with that of the SAMS composition from Example Two

FIG. 3 shows a comparison of the FT-IR scans of the SAMS compositionfrom Example One with the starting Omnifil clay

FIG. 4 shows a comparison of the FT-IR scans of the SAMS compositionfrom Example Two with the starting Hydragloss 90 clay

FIG. 5 shows the comparison of the FT-IR scans of Hydragloss 90 and SAMScompositions prepared at B/C ratios of 0.5 (Example Two), 1.0 and 2.0(Example Five, Tests No. 1 and 2, respectively)

FIG. 6 shows a comparison of the FT-IR scans of the SAMS compositions ofExample Six prepared from Omnifil clay and different mole ratio sodiumsilicate bases using a B/C ratio of 0.5

FIG. 7 shows the comparison of the FT-IR scans of the SAMS compositionsof Example Nine prepared from Hydragloss 90 and 2.5 mole ratio sodiumsilicate at B/C ratios of 0.75 to 5.0

FIG. 8 shows the comparison of the FT-IR scans of the SAMS compositionsof Example Nine prepared by the reaction of Hydragloss 90 and sodiumhydroxide at B/C ratios of 0.75 to 5.0

FIG. 9 shows the scanning electron microscope (SEM) photograph ofZeolite A

FIG. 10 Shows the SEM photograph of zeolite X

FIG. 11 Shows the SEM photograph of zeolite Y

FIG. 12 Shows the SEM photograph of analcime

FIG. 13 Shows the SEM photograph of the SAMS composition of Example One

FIG. 14 Shows the SEM photograph of the SAMS composition of Example Two

FIG. 15 Shows the TEM photograph of prior art amorphous sodiumalumino-silicate, Zeolex 23

FIG. 16 Shows the TEM photograph of prior art amorphous syntheticsilica, Hi-Sil 233

FIG. 17 Shows the TEM photograph of prior art calcined clay, Hycal

FIG. 18 Shows the TEM photograph of the SAMS composition of the presentinvention derived from Omnifil east Georgia clay at a B/C ratio of 0.75(Example One)

FIG. 19 Shows the TEM photograph of SAMS composition of Example One

FIG. 20 Shows the TEM photograph of the SAMS composition of the presentinvention derived from Hydragloss 90 east Georgia clay at a B/C ratio of0.5 (Example Two)

FIG. 21 Shows the TEM photograph of the SAMS composition of Example Two

FIG. 22 Shows the TEM photograph of the SAMS composition of the presentinvention derived from Hydragloss 90 at a B/C ratio of 1.0 (ExampleFive, Test No. 1)

FIG. 23 Shows the TEM photograph of the SAMS composition of the presentinvention derived from Hydragloss 90 at a B/C ratio of 2.0 (ExampleFive, Test No. 2)

FIG. 24 Shows the TEM photograph of the control Omnifil clay

FIG. 25 Shows the TEM photograph of the control Hydragloss 90 clay

FIG. 26 Is the XRD scan of zeolite A

FIG. 27 Is the XRD scan of zeolite X

FIG. 28 Is the XRD scan of zeolite Y

FIG. 29 Is the XRD scan of analcime

FIG. 30 Is the XRD scan of Zeolex 23

FIG. 31 Is the XRD scan of Hi-Sil 233

FIG. 32 Is the XRD scan of Hycal

FIG. 33 Is the XRD scan of the SAMS composition of Example One showingonly attenuated kaolin peaks

FIG. 34 Is the XRD scan of the SAMS composition of Example Two showingonly attenuated kaolin peaks

FIG. 35 Is the XRD scan of the SAMS composition of Example Five, Test 1showing only attenuated kaolin peaks

FIG. 36 Is the XRD scan of the SAMS composition of Example Five, Test 2showing only attenuated kaolin peaks

FIG. 37 Is the XRD scan of the starting Omnifil clay

FIG. 38 Is the XRD scan of the starting Hydragloss 90 clay

DESCRIPTION OF PREFERRED EMBODIMENTS

The synthetic alkali metal alumino-silicates (SAMS) of the presentinvention are unique products which are eminently useful as reinforcingagents or functional fillers for paper, paints, plastics, rubber andspecialty materials. The products are particularly characterized asbeing rimmed alkali metal alumino-silicate compositions which haveincreased opacity and structure, and unique morphology when comparedwith the starting clay material. Further, the brightness of theresulting product is substantially higher than the starting clay andcomparable or superior to various clay materials now used as reinforcingagents or functional fillers for paper, paints, plastics, and the like.It is truly unexpected that the opacity and brightness of the SAMScompositions would be significantly increased over the startingmaterials.

The alkali metal alumino-silicate products of the present invention alsohave unexpectedly high oil absorption characteristics, the oilabsorption in milliliters of oil per 100 grams of the SAMS productranging from about 40 to above 200 ml/100 g. This is quite remarkable inthat a hydrous clay of very low oil absorption of about 30 ml/100 g hasbeen transformed into a SAMS product of low to high structure (LS to HS)by the instant invention. For definition of structure, see Table I.

Throughout this case the product, for the sake of simplicity, isdescribed as substantially amorphous. Attenuated kaolin peaks maycontinue to be observed by x-ray diffraction although it is clear by TEMthat the kaolinite structure, to the extent it may in any case be saidto remain, has clearly been altered as seen in the TEM photographs ofFIGS. 18-21. A full theoretical explanation is not at present available.

The synthetic alkali metal alumino-silicates of this invention may bedescribed by the following general formula:

    xM.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O.

wherein x is the number of moles of alkali metal oxide and M is thealkali metal, y is the number of moles of SiO₂ present in the SAMScomposition, and z is the number of moles of bound water.

The specific SAMS products of this invention may be prepared by thefollowing reaction:

    Alkali metal silicate+kaolin=SAMS.

The B/C ratio determines the variety of SAMS compositions which can beproduced by the teachings of the instant invention as can be seen in TEMFIGS. 18 through 23. A B/C ratio of less than 1.0 is the preferredembodiment of the instant invention. Generally, at B/C ratios higherthan 1.0, along with SAMS products, zeolites are produced although SAMSof desired morphology and preferred composition can also be producedwithout the presence of zeolitic species by using desired reactionconditions.

The preferred raw materials for the preparation of unique SAMScompositions are alkali metal silicate and kaolin clay. Typically thealkali metal silicate is of the composition

    M.sub.2 O:rSiO.sub.2

where M is the alkali metal and r is the number of moles of SiO₂ boundto the moles of alkali metal oxide. When M is sodium, the alkali metalsilicates are called sodium silicates and the value of r is called themole ratio SiO₂ /Na₂ O. Typically, the sodium silicates used in the SAMSreaction have an r value of 1.0-4.0. The kaolin clay used in the SAMSreaction may be represented by the formula Al₂ O₃ :2SiO₂ :2H₂ O. It isnot essential that only kaolin may be used in the SAMS reaction.Equivalent raw materials or non-kaolin products which can provide anacceptable source of alumina or alumina-silica may also be used.

A stoichiometric equation for the formation of SAMS may be representedas follows:

    xM.sub.2 O:rSiO.sub.2 +Al.sub.2 O.sub.3 :2SiO.sub.2 :2H.sub.2 O=xM.sub.2 O:Al.sub.2 O.sub.3 :ySiO.sub.2 :zH.sub.2 O

where x is the number of moles of alkali metal silicate per mole ofkaolin clay used in the total composition of the SAMS reaction.Typically, the value of x in the SAMS product varies from 0.01 to 2. TheM is the alkali metal, y is the number of moles of SiO₂ present in theunique SAMS compositions, and z is the number of moles of bound water.

Thus when x is 0.9, y is 5.4, z is 1.0, and M is sodium, the SAMScomposition may be expressed as:

    0.9Na.sub.2 O:Al.sub.2 O.sub.3 :5.4SiO.sub.2 :H.sub.2 O.

Accordingly, when x=1.5, y=9.4, z=1.0 and M is sodium, the SAMScomposition may be expressed as:

    1.5Na.sub.2 O:Al.sub.2 O.sub.3 :9.4SiO.sub.2 :H.sub.2 O.

A particular advantageous product is obtained when the preferred sodiumsilicate is Na₂ O:rSiO₂ where r of range 1 to 4 is used as the alkalimetal silicate in the hydrothermal reaction to form the unique SAMScompositions.

The SAMS compositions are produced by the reaction of clays and alkalimetal silicates under hydrothermal conditions. The clays which may beused include all kaolin-type clays, including crude, air-floated andwater-washed clays, as well as equivalent materials. Pure clays, as wellas impure clays, may be used. Some of the preferred clays are kaolinclays sold commercially under the trademarks OMNIFIL, HYDRASPERSE, andHYDRAGLOSS. Other mineral sources corresponding to the silica-aluminavalues present in clays and alkali metal silicates may be used. Sourcesof alumina such as alumina, sodium aluminate, aluminum hydroxide orother aluminum sources may be used without deviating from the spirit ofthe instant invention. Silica sources may include synthetic silica,reactive silica, sodium silicate or equivalent materials.

The alkali metal silicate can be any of the types of materials known tothe art, but preferably sodium silicate, potassium silicate, lithiumsilicate, or mixtures thereof, or compositions which can react to giveequivalent compounds.

A critical feature of the invention is the molar ratio developed in thesystem between the amount of alkali metal silicate and the amount ofclay used. It is necessary to control the molar ratio of alkali metalsilicate to clay, otherwise a zeolitic crystalline product or mixturesof amorphous and crystalline species will be produced. The products ofthe present invention are typically rimmed compositions as depicted inTEM FIGS. 18 through 23. It is preferred that the molar ratio of alkalimetal silicate to clay be controlled to produce the desired SAMSproduct.

Further, the reaction of the present invention is carried out in anaqueous system using an aqueous slurry of the clay which is mixed withan aqueous solution of alkali metal silicate. The clay and alkali metalsilicate slurry preferably has a concentration of 1 to 20 weightpercent, preferably 5 to 15 percent.

In a preferred operation of the process, an aqueous slurry of thestarting clay material is mixed with the alkali metal silicate solution,the system is closed and heat applied to gradually raise thetemperature. In general, the pressure in the system will range fromabout 50 to 360 psig at temperatures ranging from about 140 to 250degrees C. A specifically preferred range of conditions is to operatethe process at pressures of 100 to 200 psig and temperatures of 164 to194 degrees C. The reaction time is about 0.25 to 4 hours. Aftercompletion of the reaction, heat is removed and the mixture is allowedto cool, after which the system is opened, the product separated byfiltration or centrifugation, washed with water, and dried.

The resulting product may be characterized as having oil absorptionvalues ranging from about 40 to above 200 ml/100 g. The surface arearanges from about 2 to 300 m² /g.

EXAMPLES

The following examples are presented to illustrate the invention, but itis not considered to be limited thereto. In the examples and throughoutthe specification, parts are by weight unless otherwise indicated.

EXAMPLE ONE Synthesis of Sams from Omnifil Clay

Water, 1,508 gallons (12,629 pounds), was added to a 2,500 gallonpressure reactor. To the water was added 101.3 gallons (1,458 pounds) ofa 67.7% solids kaolin clay slurry which is sold commercially as Omnifilby the J. M. Huber Corporation. This is a water-refined kaolin clayproduced from the East Georgia deposit having the properties shown inTable II. To the clay-water slurry was added 147.2 gallons of a freshwater sodium silicate solution (1,700 pounds) of 34.9% solids having aSiO₂ /Na₂ O molar ratio of 2.5. Under these conditions, the finalproduct solids will be approximately 10% and the batch composition willhave a base to clay molar ratio of approximately 0.75. The batchcomposition for the reaction can be expressed as

    Na.sub.2 O:1.33Al.sub.2 O.sub.3 :5.21SiO.sub.2 :278H.sub.2 O

and has an H/N (moles water/moles Na₂ O) ratio of 278, a S/N (moles SiO₂/moles Na₂ O) ratio of 5.2 and a S/A (moles SiO₂ /moles Al₂ O₃) ratio of3.9.

The batch was heated to a reaction pressure of 120 psig and atemperature of 172 degrees C. The mixture was allowed to react for onehour under continuous agitation. At the end of the one-hour reactiontime, the mixture was vented into a drop tank and the resulting mixturewas then filtered, washed and spray dried.

The product of Example One was evaluated and characterized by varioustest methods. The physical properties of the resulting synthetic alkalimetal alumino-silicate composition, or SAMS, representing the presentinvention are listed in Table II. The properties of the starting Omnifilclay control are also listed in Table II for comparative purposes.

                  TABLE II                                                        ______________________________________                                        SYNTHESIS OF SAMS FROM OMNIFIL CLAY                                                          SAMS from Omnifil                                                             Omnifil Clay                                                                            Clay Control:                                        ______________________________________                                        Chemical Analysis, %                                                          TiO.sub.2        1.43        2.12                                             Fe.sub.2 O.sub.3 0.81        1.11                                             SiO.sub.2        52.82       44.33                                            Al.sub.2 O.sub.3 24.32       37.60                                            Na.sub.2 O       7.35        0.03                                             Physical Properties:                                                          Loss on Ignition, %                                                                            10.90       13.40                                            Pore Volume, cc/g                                                                              3.10        1.10                                             (Mercury Intrusion)                                                           Surface Area, m.sup.2 /g                                                                       19.8        20.0                                             pH (at 20% Solids)                                                                             10.8        6.5                                              Oil Absorption, ml/100 g                                                                       136         37                                               Valley Abrasion, 8.7         10.5                                             (mg of wire loss)                                                             Cation Exchange Capacity,                                                     meq/100 g NH.sub.4.sup.+, K.sup.+                                                              186         2-3                                              meq/100 g Ca.sup.+2, Mg.sup.+2                                                                 45          1-2                                              Brightness, %    86.1        82.0                                             Sedigraph Particle Size, %:                                                    +10 microns     0.5         1.8                                                +5 microns     3.0         4.0                                                -2 microns     58.5        89.0                                               -1 micron      34.0        82.9                                             -0.5 micron      15.0        68.1                                             ______________________________________                                    

EXAMPLE TWO Synthesis of Sams from Hydragloss 90 Clay

A second reaction was conducted in which 1,500 gallons (12,562 pounds)of water was used with 110 gallons (1,613 pounds) of a 70.1% solidskaolin clay slurry sold commercially as Hydragloss 90 by J. M. HuberCorporation having the properties shown in Table III. To the clay-waterslurry was added 112.4 gallons of a fresh water sodium silicate solution(1,298 pounds) of 34.9% solids having a SiO₂ /Na₂ O molar ratio of 2.5.Under these conditions, the final product solids will be approximately10% and the batch composition will have a base to clay molar ratio ofapproximately 0.50. The batch composition for the reaction can beexpressed as

    0.76Na.sub.2 O:1.52Al.sub.2 O.sub.3 :4.94SiO.sub.2 :278H.sub.2 O

and has an H/N of 366, and S/N of 6.5 and an S/A of 3.25.

The batch was heated to a reaction pressure of 120 psig and atemperature of 172 degrees C. The mixture was allowed to react for onehour under continuous agitation. At the end of the one-hour reactiontime, the mixture was vented into a drop tank and the resulting mixturewas then filtered, washed, and spray dried.

The product of Example Two was subjected to various tests. Set forthhereinafter in Table III are the physical properties of the resultingsynthetic alkali metal alumino-silicate composition, or SAMS,representing the present invention and the kaolin clay control fromwhich the SAMS composition was prepared.

                  TABLE III                                                       ______________________________________                                        SYNTHESIS OF SAMS FROM HYDRAGLOSS 90 CLAY                                                    SAMS from Hydragloss 90                                                       Hydragloss 90                                                                           Clay Control                                         ______________________________________                                        Chemical Analyses, %                                                          TiO.sub.2        0.51        0.94                                             Fe.sub.2 O.sub.3 0.83        0.98                                             SiO.sub.2        54.57       44.79                                            Al.sub.2 O.sub.3 27.95       38.37                                            Na.sub.2 O       6.75        0.03                                             Physical Properties:                                                          Loss on Ignition, %                                                                            10.71       13.86                                            Pore Volume, cc/g                                                                              3.56        0.86                                             (Mercury Intrusion)                                                           Surface Area, m.sup.2 /g                                                                       21.5        22.0                                             pH (at 20% Solids)                                                                             11.2        6.8                                              Oil Absorption,  156         43                                               ml/100 gm                                                                     Valley Abrasion, 6.8         7.5                                              (mgs of wire loss)                                                            Cation Exchange Capacity:                                                     meq/100 g - NH.sup.+ 4, K.sup.+                                                                183         2-3                                              meq/100 g - Ca.sup.+2, Mg.sup.+2                                                               48          1-2                                              Brightness, %    92.6        91.0                                             Sedigraph Particle Size, %                                                     +10 microns     0.0         0.0                                                +5 microns     0.0         0.0                                                -2 microns     61.0        98.0                                               -1 micron      37.0        96.1                                             -0.5 micron      18.0        84.7                                             ______________________________________                                    

The following procedures were used for characterizing the data listed inTables II and III.

Chemical analyses (% TiO₂, % Fe₂ O₃, % SiO₂, % Al₂ O₃) were determinedby x-ray fluorescence. The sodium content (Na₂ O) of the final productwas determined by atomic absorption.

Ignition loss was determined by pre-drying the SAMS product to aconstant weight at 110 degrees C., heating to 925 degrees C. for onehour and cooling. Calculations of ignition loss were made as follows:##EQU3##

The pH was measured using a standard pH meter on a 20% solids (byweight) mixture of the product with water.

The specific surface area was determined by the nitrogen absorptionmethod described by Brunauer, Emett, and Teller (BET) in the "Journal ofthe Americal Chemical Society," Volume 60, page 309, published in 1938.A single point surface area determination was made on the SAMScompositions using outgassing conditions of three hours at 300 degreesC.

The oil absorptions of the beginning and end products from Examples Oneand Two were determined by the oil rub-out method. This method is basedon a principle of mixing linseed oil with the product by rubbing with aspatula on a smooth surface until a stiff putty-like paste is formedwhich does not break or separate. By measuring the quantity of oilrequired to give a paste mixture which will curl when spread out, onecan calculate the oil absorption value of the product-a value whichrepresents the volume of oil required per unit weight of product tosaturate the product sorptive capacity. Calculation of oil absorptionvalue was done as follows: ##EQU4##

Cation exchange capacity was determined by adding the products (0.25g-weighed to 0.1 mg) to tarred, screw-cap, 15-ml centrifuge tubes. Thesamples were centrifugally washed three times with 10-ml of a 0.5Msolution of the saturating cation. The samples were subsequently washedfive times with a 0.05M solution of the saturating cation. Following thefifth washing and decantation of the supernatant solution, the tubeswere capped and weighed. This weight, less the sample weight, representsthe amount of excess 0.05M saturating solution. The occluded (soluble)and exchangeable cations were then displaced by washing three times witha 0.5M solution of a displacing cation, collecting the washings in 100ml volumetric flasks. The amount of the saturating cation was determinedby atomic absorption spectroscopy with the exception of ammonium (NH⁺ ₄)which was determined by potentiometric titration. The net amount ofexchangeable cations was calculated by subtracting the amount ofsoluble, occluded cations (wet weight times 0.05M) from the totalanalyzed amount.

Brightness measurements were performed by the standard TAPPI (TechnicalAssociation of Pulp and Paper Industry) procedure T-534 pm-76, publishedin 1976.

Particle size was determined using a Sedigraph 5000 ET Particle SizeAnalyzer from Micromeritics Instrument Corporation, Norcross, Ga. Thisinstrument uses a sedimentation technique which measures the particlesize distribution as a modification of Stokes Law. The procedure isdescribed in "Instrument Manual-Sedigraph 5000 ET Particle SizeAnalyzer," published May 3, 1983.

The Fourier Transform-Infrared spectroscopy (FT-IR), transmissionelectron microscopy (TEM), scanning electron microscopy (SEM and x-raydiffraction (XRD) scans were determined using standard techniques.

From the above data, it will be seen that the process of the inventionyields new products having novel combinations of physical and chemicalproperties.

As shown in Tables II and III, the synthetic alkali metalalumino-silicates of the present invention prepared from the commercialkaolin clays exhibit substantial improvements in cation exchangecapacity, oil absorption and brightness. This is quite astonishing inthat a hydrous clay product of relative worth has been converted into asynthetic product of greatly added value by the relatively simpleprocedure of the present invention. Of particular interest is thesignificant improvement in oil absorption which indicates that a higherstructure product has been formed as a result of this invention.

The infrared spectra of the SAMS compositions of Examples One and Twoare compared with the infrared spectra of their respective base clays inFIGS. 3 and 4, respectively. As anyone skilled in infrared spectroscopycan see, the IR spectra of SAMS compositions are considerably differentfrom those of their respective base clays, especially in the 1200-875wavenumber (cm⁻¹) absorption region. The Si-O stretching band between1200 and 950 wavenumbers is much broader and less well defined for theSAMS than for the control clays, indicating that the compositionscontain considerable amorphous material. In addition, the aluminum O--Hvibration band between 950 and 875 wavenumbers are essentially identicalfor the SAMS compositions and their base clays, with the SAMScomposition showing only a slight decrease in peak intensity.

In FIG. 1, the FT-IR scan of the SAMS composition of Example Two iscompared with the FT-IR scans of an amorphous synthetic silicate (Zeolex23), a calcined kaolin (Hycal) and an amorphous synthetic silica (Hi-Sil233). The spectrum of the SAMS composition is similar to those of Zeolex23, Hycal, and Hi-Sil in the 1200-950 wavenumber Si-O stretching regionbut is considerably different in the 950-400 wavenumber region. Only theSAMS composition has the aluminum O--H vibration band between 950 and875 wavenumbers.

In FIG. 2 the FT-IR spectrum of the SAMS composition of Example Two iscompared with the spectra of zeolites A, X, Y and analcime. The spectrumof the SAMS composition differs from the spectra of the crystallinezeolites across the entire IR spectrum. The Si-O band (1200-950 cm⁻¹)for the zeolites is very sharp, indicating good crystallinity, whilethat of the SAMS is broad. Again, only the SAMS spectrum shows thealuminum O--H vibration band.

Based on the infrared spectra, it must be concluded that the SAMScompositions of the instant invention are unique entities that differsignificantly from the starting clays as well as from crystalline andamorphous zeolites, synthetic silicates and synthetic silicas of priorart.

The unique characteristics of the synthetic alkali metalalumino-silicates (SAMS) of the instant invention can also be seen bycomparing the SEM photographs of the SAMS compositions of Example Oneand Two (FIGS. 13 and 14, respectively) with those of prior art zeolitesA, X, Y and analcime (FIGS. 9, 10, 11 and 12, respectively). The SEMphotographs show the prior art zeolites to be large, well crystallizedmaterials, while the SAMS compositions appear to be structuredagglomerates composed of small flat platelets.

The TEM photographs of the SAMS compositions of Example One and Two,prepared by following the preferred teachings of the instant invention(B/C less than 1.0), and the photographs of SAMS compositions preparedat B/C ratios equal to and greater than 1.0 can be seen in FIGS. 18through 23, respectively, and show the SAMS to be unique in compositionand morphology. The TEM photographs (FIGS. 18-23) show the SAMScompositions to contain remnants of altered clay platelets having anintegrated rimmed area of alkali metal silicate-kaolin reaction product.The rimmed area can be shown by electron diffraction (ED) to beamorphous and non-diffracting. The SAMS compositions shown in FIGS.18-23, are unique and considerably different in appearance than thestarting Omnifil and Hydragloss 90 clay (FIGS. 24 and 25, respectively),as well as the prior art silicates, silicas, and calcined clays shown inFIGS. 15-17.

When comparing the x-ray diffraction patterns of the SAMS compositionsof Examples One, Two and Five (FIGS. 33-36) with the XRD patterns of thestarting clays (FIGS. 37 and 38), only attenuated kaolin peaks from thekaolin remnants can be observed. The XRD patterns of the SAMScompositions are also obviously different than the XRD patterns of theprior art zeolites, silicates, silicas, and calcined clay shown in FIGS.26-32.

END-USE APPLICATIONS

The novel SAMS products of the present invention were evaluated in avariety of end-use application compositions. Truly remarkableperformance of SAMS products are documented below.

1. Paper Coating Compositions

The SAMS product of Example Two derived from Hydragloss 90 clay wasevaluated in a typical paper coating composition and evaluation data areshown in Table IV.

A coating is applied to a paper substrate primarily to improve printingquality, although improvements in optical properties such as brightnessor sheet gloss may also be obtained. The SAMS product made fromHydragloss 90 in Example Two was included at low levels in coatingcompositions and compared with a composition using only a commercialgrade of delaminated kaolin clay (Hydraprint), and a compositioncontaining the delaminated clay and a low level of a commerciallyavailable, high brightness, low abrasion calcined clay (Hycal), in anapplication for lightweight publication grade paper. The end-use of thisparticular paper and its coating formulation was in the art of printingby the rotogravure method. Coatings were applied to a commerciallyproduced paper substrate at a coat weight typical to the grade using theKeegan Laboratory Blade Coater. Following supercalendering, coatedsheets were tested for optical properties in accordance with thefollowing TAPPI (Technical Association of Pulp and Paper Industry)standards:

T-452: Brightness of Pulp, Paper and Paperboard

T-480: Specular Gloss of Paper and Paperboard at 75 degrees Rotogravureprintability was determined using the Diamond National Print SmoothnessTester. The procedure followed is to coat, calender and print papersamples by the rotogravure method with a series of lines composed ofdots. The dots are the result of printing cells engraved on therotogravure printing cylinder, each of identical diameter and depth. Thenumber of dots which do not transfer to the sheet is determined, withthe greater number of missing dots being interpreted as poorerrotoogravure printability.

As noted from Table IV, when used at one-half the loading level ofcalcined clay, the product of the current invention unexpectedlyproduced a sheet of equivalent rotogravure printability, and clearlysuperior to that where only delaminated clay was used. Thus, one part ofthe product of the current invention can replace two parts of calcinedclay resulting in substantial cost savings for those skilled in the artof paper coating. Furthermore, when used at an equal loading level withthe expensive calcined clay, the SAMS product of this invention yieldeda sheet of comparable optical properties, and clearly superiorrotogravure printability.

                                      TABLE IV                                    __________________________________________________________________________    PAPER COATING COMPOSITIONS CONTAINING SAMS                                               100%  90% Hydraprint                                                                          90% Hydraprint  95% Hydraprint                                Hydraprint                                                                          10% Calcined Clay                                                                       10% SAMS from Example Two                                                                     5% SAMS from Example               __________________________________________________________________________                                               Two                                Brightness, %                                                                            68.2  69.2      69.0            68.7                               75 Degree Gloss, %                                                                       43.7  45.0      45.5            44.0                               Missing Dots/Sheet*                                                                      31    22        15              23                                 __________________________________________________________________________     *Diamond National smoothness test                                        

2. Fine Paper Filler Compositions

Pigments are used as fillers in paper sheets for many reasons, amongwhich are the improvement of optical properties such as brightness andopacity. The most efficient pigment for this purpose is titaniumdioxide; however, its price is prohibitive for its sole use in thisapplication. A class of pigments, known as titanium dioxide extenders,are less expensive, but still quite costly. When used in combinationwith titanium dioxide, these pigments allow for reduced titanium dioxideuse while maintaining optical properties. Two pigments from this groupwhich are quite effective are calcined kaolin clay and amorphous sodiumsilico-aluminate (Hydrex) pigments. The SAMS product made fromHydragloss 90 in Example Two was substituted directly for the titaniumdioxide extender pigments, calcined clay (Hycal) and sodiumsilico-aluminate (Hydrex), in a filler furnish containing 50% No. 2grade clay (Hydrasperse), 17% titanium dioxide (DuPont LW), and 33%extender pigment. Handsheets were formed using the British StandardHandsheet Mould, weighed to assure uniform basis weight, and testedaccording to the prescribed TAPPI standards:

T-425: Opacity of Paper

T-452: Brightness of Pulp, Paper, and Paperboard

Additionally, the scattering and absorbance coefficients (S and K,respectively) were determined using the Kubelka-Munk equation. The valueK/S was then determined, and presented as the scattering efficiency.Greater efficiency is noted as the K/S value approaches zero. Thecomparative evaluation data of SAMS and other extender pigments used inthe paper filler composition is given in Table V.

It will be noted from Table V that the product of the current inventioncompares favorably to the expensive extender pigments in all parametersat each filler loading level. This is quite surprising in that the SAMSproducts of the present invention can be a match for the most expensiveextender pigments normally used by the paper industry.

                                      TABLE V                                     __________________________________________________________________________    FINE PAPER FILLER COMPOSITIONS CONTAINING SAMS                                                               Light Scattering                                               Filler,                                                                           Brightness,                                                                         Opacity,                                                                           Efficiency,                                                    %   %     %    K/S × 10.sup.-2                          __________________________________________________________________________    Unfilled Control                                                                              0   82.5  71.8 1.87                                           50% No. 2 Clay  2   84.3  74.4 1.46                                           17% Titanium Dioxide                                                                          4   85.4  78.5 1.25                                           33% Calcined Clay (Hycal)                                                                     8   86.0  81.2 1.14                                           50% No. 2 Clay  2   84.8  73.9 1.36                                           17% Titanium Dioxide                                                                          4   85.5  78.2 1.23                                           33% Hydrex      8   86.2  81.6 1.10                                           50% No. 2 Clay  2   85.0  75.2 1.32                                           17% Titanium Dioxide                                                                          4   85.4  78.1 1.25                                           33% SAMS from Example Two                                                                     8   86.0  81.5 1.14                                           __________________________________________________________________________

3. Newsprint Paper Compositions Containing SAMS

Another function of fillers in uncoated paper is to retard the amount ofink which penetrates the sheet, causing discoloration to the other sideof the paper. This problem, frequently referred to as "printshow-through" or "print through," is generally encountered in newspaperprinting. Improvement in this property is of more concern as qualitystandards for newsprint and similar grades continue to tighten.

The SAMS products made from Omnifil and Hydragloss 90 clays in ExamplesOne and Two are compared with their respective starting materials, to acommercial grade of high brightness, low abrasion calcined kaolin clay(Ansilex), and to a high brightness sodium silicoaluminate (Zeolex 23P)in their ability to reduce show-through. Handsheets were prepared fromcommercial newsprint pulp using a Noble and Wood sheet machine, andtested in accordance with the following TAPPI standards:

T-410: Basis Weight of Paper and Paperboard

T-425: Opacity of Paper

T-452: Brightness of Pulp, Paper and Paperboard

Additionally, printing tests were performed at standard conditions oftemperature and humidity on a Universal No. 1 Vandercook Proof Pressusing a standard newsprint ink and a printing plate mounted type high.The plate was designed for printing a solid area 4 inches by 41/4inches. Prints were made with 4 mils impression by press bed adjustment,and the ink pickup determined by weighing each sheet before and afterprinting. Variations in printing and ink pickup necessitated printingeach ash level at three ink levels, and obtaining printing values atexactly 2.0 g/m² ink pickup graphically.

Printed sheets were conditioned overnight at 73 degrees F. and 50%relative humidity prior to evaluation by a brightness tester at 457 nmon the side opposite the printing surface. Show-through was determinedin accordance with Larocque's equation: ##EQU5##

Comparative data on the newsprint evaluation of SAMS and other expensiveextender pigments are given in Table VI.

                                      TABLE VI                                    __________________________________________________________________________    NEWSPRINT EVALUATION OF SAMS AND OTHER EXTENDER PIGMENTS                               Filler                                                                            Basis                                                                              TAPPI      Show-Through                                     Filler   Level,                                                                            Weight,                                                                            Brightness,                                                                         Opacity,                                                                           @2 g/m.sup.2                                                                       Reduction,                                  Pigment  %   #/ream                                                                             %     %    Ink, %                                                                             %                                           __________________________________________________________________________    Unfilled None                                                                              30.6 52.9  85.1 10.8 --                                          Omnifil (Control)                                                                      2   30.3 52.9  85.1 12.6 (16.7)                                               4   30.4 60.0  85.5 11.7 (8.3)                                       Hydragloss 90                                                                          2   30.5 59.4  85.1 13.1 (21.3)                                      (Control)                                                                              4   30.1 60.6  85.4 12.8 (18.5)                                      Ansilex  2   29.8 60.5  85.6 10.8 0                                           (Calcined Clay)                                                                        4   30.1 62.0  87.4 9.1  15.7                                        Zeolex 23P                                                                             2   30.4 60.2  85.5 9.1  15.7                                        (Sodium: Silico-                                                                       4   30.4 61.3  86.5 6.4  40.7                                        Aluminate)                                                                    SAMS from                                                                              2   30.3 59.9  86.3 9.6  11.1                                        Example One                                                                            4   30.7 61.9  88.0 7.0  35.2                                        SAMS from                                                                              2   30.3 60.5  86.4 8.7  19.4                                        Example Two                                                                            4   30.6 62.0  88.5 6.8  37.0                                        __________________________________________________________________________

It is seen in Table VI that the SAMS product from Example Two performsas well as the calcined clay and superior to the other pigments inbrightness improvement, and is also the superior pigment in opacityimprovement. The SAMS product from Example One is surprising in itsperformance as well. Its opacity is second only to the product made fromExample Two, exceeding both of the other higher brightness pigments,Ansilex and Zeolex 23. Concerning show-through, it can be noted fromTable VI that the use of the starting hydrous clay materials (Omnifiland Hydragloss 90) actually result in more show-through than observedwith the unfilled sample. The use of calcined clay, while improvingshow-through modestly at 4% filler loading, leaves the sheet unchangedfrom unfilled at the 2% filler level. When the products of the currentinvention are substituted directly at the 2% filler level for the Zeolex23 pigment, that pigment being the product of choice for this purpose incommercial applications, the results were indeed surprising. The SAMSproduct from Example Two actually surpasses the Zeolex 23 pigment, whilethat made in Example One is only slightly deficient. Although theproducts of the current invention are slightly less efficient than theZeolex 23 at the higher loading level, they are clearly superior totheir starting inexpensive clay controls and to the expensive calcinedclay. Furthermore, due to the high cost of the Zeolex 23 pigment, it canbe easily shown that the cost per unit of strike-through reduction forthe products of the present invention is much more favorable than thatof the Zeolex 23. Thus, if used at quantities sufficient for equalstrike-through reduction, the products of the current invention wouldprovide significant cost savings in this application.

4. Latex Paint Compositions Containing SAMS

In the past, functional extender pigments were primarily used in paintas adulterants to replace more expensive prime pigments and binders;thereby resulting in a lower cost paint formulation. However, with theadvent of new and improved functional extender pigments, the use ofthese pigments has grown. They are now incorporated into the paintformulations to improve optical properties such as whiteness, hidingpower/contrast ratio, and tinting strength.

In this regard, the SAMS product made from Hydragloss 90 in Example Twowas compared with the kaolin clay from which the SAMS composition wasprepared and leading commercial pigments used as functional extenders inlatex-based paints.

Whiteness (directional reflectance, Y-value) and contrast ratio weredetermined by making drawdowns of the paints containing control clay(Hydragloss 90), the SAMS product from Example Two made from Hydragloss90, a commercial extender pigment (Hi-Sil 422), and calcined clay (Huber90C), on opacity charts having a simple combination of black and whiteareas large enough for reflectance measurements. Such charts aresupplied by the Leneta Company, Ho-Ho-Kus, New Jersey. Directionalreflectance, Y values, are determined using a Gardner XL-20 TristimulusColorimeter on the dried paint films over both the black and white areasof the charts. Whiteness is reported as the Y value determined over thewhite area. Contrast ratio is determined by dividing the Y values overblack areas by the Y values over the white areas of the charts and is ameasure of the relative opacity of the paint.

Relative tint strength was determined by blending 1%, by weight, of alamp black colorant to each paint, making drawdowns on the opacitycharts and then determining Y values of the dried paint films over thewhite areas of the charts. Relative tint strength is reported as this Yvalue.

Comparative paint performance results of unique SAMS products and otherexpensive extender pigments are contained in Table VII.

                  TABLE VII                                                       ______________________________________                                        LATEX PAINT EVALUATION OF SAMS AND                                            OTHER PIGMENTS                                                                               Whiteness                                                                     (Directional                                                                             Con-    Relative                                                   Reflectance,                                                                             trast   Tint                                        Pigment        Y-Value, %)                                                                              Ratio   Strength, %                                 ______________________________________                                        Hydragloss 90, Control                                                                       87.9       .944    38.8                                        SAMS from Example Two                                                                        88.8       .958    41.0                                        Hi-Sil 422     88.7       .947    40.8                                        Huber 90C      88.6       .949    40.5                                        ______________________________________                                    

Regarding Table VII, it will be noted that the control clay Hydragloss90 and the commerical products, Hi-Sil 422 (fine particle hydratedsilica pigment), and Huber 90C (high brightness, low abrasion calcinedclay) are compared with the Hydragloss 90 product of Example Two withrespect to whiteness, contrast ratio and tint strength. The variouspigments were evaluated in a typical high pigment volume concentration,interior, flat, vinyl acrylic paint. Pigmentation of the paint consistedof 17.6% rutile titanium dioxide, 19.6% standard calcined clay, 58.8%coarse particle-size calcium carbonate, and 4.0% of the evaluatedpigment. It will be noted from Table VII that the SAMS product of thisinvention produces significant improvements over the kaolin clay fromwhich the product of this invention was prepared in whiteness, contrastratio and relative tint strength. Even more unexpectedly, the product ofthis invention gave an enhanced contrast ratio and superior tintstrength to the more costly functional extender, Hi-Sil 422.

Additionally, as can be seen from Table VII SAMS products of the presentinvention exhibit the best whiteness, contrast ratio (or hiding power)and tint strength when compared with expensive commercial extenderpigments. It is truly remarkable how the inexpensive starting clay hasbeen converted into a functional product SAMS by the teachings of thepresent invention.

5. Natsyn 2200 Rubber Compositions Containing Sams

Fillers are added to rubber compounds to provide reinforcement or act asa diluent. Small particle substances are considered to reinforce rubberif they give to the vulcanizate high abrasion resistance, high tear andtensile strength, and some increase in stiffness. The most importantcharacteristic required of a reinforcement agent is a fine particlesize. Among non-black fillers, the best modulus and tensile strength areproduced by precipitated silica (Hi-Sil), followed by synthetic sodiumsilico-aluminate (Zeolex). Fine particle size fillers that areapproximately spherical in shape, such as many silicas, give better tearresistance and abrasion resistance to rubber than do needle-shaped orplate-like particles.

SAMS from Examples One and Two were evaluated in rubber compositions andtheir performance compared with the more expensive fine particleprecipitated, hydrated amorphous silica product, Hi-Sil 233.

The rubbers which can be employed in the invention include both naturaland synthetic rubbers. Exemplary of suitable synthetic rubbers arestyrene-butadiene, butyl rubber, nitrile rubber, neoprene rubber,polybutadiene, polyisoprene, ethylene propylene, acrylic, fluorocarbonrubbers, polysulfide rubbers, and silicone rubbers. Mixtures ofcopolymers of the above synthetic rubbers can be employed alone or incombination with natural rubber. The most preferred rubbers are naturalrubber, polyisoprene, nitrile rubber, styrene-butadiene, and mixturesthereof.

The SAMS product made from Hydragloss 90 in Example Two was evaluatedagainst a fine particle precipitated, hydrated amorphous silica product(Hi-Sil 233) in a non-black synthetic polyisoprene (Natsyn 2200) rubberformulation.

The SAMS and silica products were used at a 38-40 part level per 100parts rubber. The filler products were compared with respect to modulusand tensile strength (ASTM D1456), heat buildup (rectangular blockoscillating horizontally between two weights), compression set (ASTM395--ability of rubber compounds to retain elastic properties afterprolonged action of compressive stresses), and tear strength (ASTM 624).

Evaluation results of the reinforcing properties of SAMS and acommercial expensive synthetic silica, Hi-Sil 233, are listed in TableVIII.

                  TABLE VIII                                                      ______________________________________                                        NATSYN RUBBER REINFORCING PROPERTIES                                          OF SAMS                                                                                               SAMS from                                                           Hi-Sil 233                                                                              Example Two                                           ______________________________________                                        300% Modulus, psi*                                                                            460         630                                               Tensile Strength, psi*                                                                        2,850       2,870                                             Heat Buildup, Degrees F.                                                                      267         136                                               Tear Strength, ppi                                                                            140         155                                               Compression Set, %                                                                            41.6        23.2                                              ______________________________________                                         *10 Minute cure                                                          

It will be noted from the Table VIII that the SAMS product of thisinvention is superior to the amorphous silica product in modulus,compression set, and heat buildup, where the silica product has twicethe heat buildup when compared with SAMS products of the presentinvention. It is truly remarkable that the inexpensive clay has beenconverted into a unique functional SAMS composition. This uniqueproperty of low HBU (heat buildup) causes the product to have particularutility for use in tires, hoses, and belts where lower heat generationfrom friction will substantially prolong the longevity of theseproducts. In this regard, the synthetic alkali metal alumino-silicatesof this invention can also be used gainfully in elastomeric applicationswhere exposure to high temperatures can cause severe deterioration ofstandard elastomeric systems.

The tire industry has been looking for a reinforcing filler which willprovide low heat buildup in rubber formulations. As data clearly showsin Table VIII, the heat buildup imparted by SAMS of the presentinvention is almost one-half that of the commercial expensive silica,Hi-Sil 233. The control structure of the unique SAMS ompositions isresponsible for providing excellent rubber reinforcing properties.

6. Giant Tire Rubber Compositions Containing SAMS

The SAMS products made from Omnifil and Hydragloss 90 in Example One andTwo were evaluated against a fine particle, precipitated, hydratedamorphous silica product (Hi-Sil 233) in an off-the-road giant tiretread natural rubber formulation containing N220 carbon black. The SAMSand silica products were used at a 15 part level and the N220 carbonblack at a 40 part level per 100 parts of rubber.

The filler products were compared with respect to modulus, tensilestrength, tear strength, heat buildup, and a flex fatigue failure test(ASTM D1052--Ross flexing machine that allows a pierced rubber specimento bend freely over a rod through an angle of 90 degrees for the numberof cycles required for specimen failure). It will be noted from the testresults of Table IX that the SAMS products of this invention fromOmnifil and Hydragloss 90 are equal or superior to the high-pricedamorphous silica product in modulus, tensile strength, tear strength,heat buildup, and flex fatigue. Of particular interest is the startlingincrease in flex fatigue property which should be very important inelastomeric systems in which a great deal of bending and stretchingstresses are involved, such as shock suppressors, hoses and tubing,bushings, etc.

By examining the evaluation data in Table IX, it can be clearly seenthat the unique SAMS products provide excellent flex fatigue protectionto rubber compositions when compared with the expensive commercialsilica products, Hi-Sil 233.

It is quite remarkable that the inexpensive clay products have beenconverted to more useful value-added materials called SAMS by theteachings of the instant invention. The performance properties of SAMSin rubber compositions are unique and quite unexpected. It appears thatthe novel SAMS compositions of the present invention are controlledstructures in nature and provide optimum filler-polymer interaction inrubber compositions.

                  TABLE IX                                                        ______________________________________                                        GIANT TIRE RUBBER REINFORCING PROPERTIES                                      OF SAMS                                                                                   Hi-Sil                                                                              SAMS From                                                               233   Example One                                                                              Example Two                                      ______________________________________                                        300% Modulus, psi*                                                                          1,360   1,490      1,500                                        Tensile Strength, psi*                                                                      3,700   3,780      3,870                                        Tear Strength, ppi                                                                            605   575        625                                          Heat Buildup,   278   267        260                                          Degrees F.                                                                    Flex Fatigue, (Cycles                                                                         471   835        666                                          To Failure × 1000)                                                      ______________________________________                                         *90 Minutes Cure                                                         

7. COLOR CONCENTRATE PLASTICS COMPOSITIONS

Pigments, fillers and extenders are mixed with plastics resins toproduce color concentrates. Titanium dioxide and colored pigments arewidely used to produce pigmented plastics concentrates.

A study was undertaken in which a 50% TiO₂ concentrate was produced inhigh density polyethylene (HDPE) resin. This concentrate was called thecontrol concentrate.

The SAMS product from Example Two was used to extend TiO₂ of the controlconcentrate by replacing 10 and 20% by weight of the TiO₂ with SAMS. Thefollowing plastic compositions were used to produce the variousconcentrates.

    ______________________________________                                        Ingredients                                                                             Control   Concentrate A                                                                             Concentrate B                                 ______________________________________                                        HDPE      50        50          50                                            R-101 (TiO.sub.2)                                                                       50        45          40                                            SAMS (from                                                                              --         5          10                                            Example Two)                                                                  ______________________________________                                    

The control and concentrates A and B containing 5% and 10% SAMS werecompounded in the 3# Farrel Banbury. Each sample was then granulated,extruded and pressed out for testing. The optical properties of thevarious concentrates were then evaluated.

The opacity and brightness of the control and SAMS containingconcentrates are listed in Table X. This study suggests that SAMS of theinstant invention can be used in color concentrates without loss inopacity and brightness.

Data are listed in Table X.

                  TABLE X                                                         ______________________________________                                        PLASTIC COLOR CONCENTRATES CONTAINING SAMS                                                       Elrepho                                                                       Brightness,                                                                             Opacity,                                         Concentrate        %         %                                                ______________________________________                                        TiO.sub.2 - Control                                                                              89.1      0.980                                            Concentrate A (w/SAMS)                                                                           91.8      0.985                                            Concentrate B (w/SAMS)                                                                           91.4      0.990                                            ______________________________________                                    

8. Defoamer Compositions

Defoamer compositions are used to suppress foam formation in the paper,paint, food and many specialty industries.

Defoamer compositions were prepared by using the following formulations:

    ______________________________________                                        Ingredients        Parts (by weight)                                          ______________________________________                                        Dow 3011 Antifoam Chemical                                                                       4.0                                                        Ammonium Carbonate 1.0                                                        Mineral Oil        200.0                                                      HG 90 or SAMS      10.0                                                       (from Example Two)                                                            ______________________________________                                    

The mineral oil called for in the above formulation was weighed out andplaced in a stainless steel cup. Control clay or SAMS from Example Twowas hand-mixed with the mineral oil. This mixture was dispersed on aHockmeyer mixer for five minutes at 2300 rpm speed. The antifoamchemical was then added, followed by ammonium carbonate. The wholecomposition was mixed for an additional three minutes.

The contents of the stainless steel cup were transferred into a 500 mlflask and heated at 80 degrees C. until the foaming stopped. Thetemperature was then increased to 105 degrees C. and the compositionmaintained at this temperature for two hours. The flask was removed fromthe hotplate and after cooling, the contents were transferred to aone-half pint can for storage. At this point the defoamer composition isready for evaluation.

The defoamer composition was checked for foam suppression properties.One liter of black kraft liquor (15% solids) was poured into a 2500 mlburette which was hooked up to a gravity feed circulating pump flowingat the rate of five liters per minute.

While the black liquor was at rest, 0.02 g (or two drops) of thedefoamer composition was added to the burette. The pump and a stop watchwere simultaneously started to record the time it takes the foam heightto reach six inches from starting point of liquor at rest. A defoamercomposition which suppresses the foam from reaching a six-inch heightfor the longest time is considered the best defoamer compound.

Defoamer efficiency data are given in Table XI.

                  TABLE XI                                                        ______________________________________                                        DEFOAMER COMPOSITIONS                                                         Defoamer Compositions                                                                            Six-Inch Suppression Time                                  ______________________________________                                        Compound w/HG-90 - Control                                                                        27 seconds                                                Compound w/SAMS    233 seconds                                                (from Example Two)                                                            ______________________________________                                    

From data in Table XI, it is clear that SAMS makes an excellent defoamerwhen compared with the starting clay. In fact, the defoaming efficiencyof SAMS from Example Two is about 762% better than the Hydragloss 90control. It is truly remarkable that the present invention has convertedthe Hydragloss 90 clay into a valued added SAMS product of uniqueefficiency for use in defoamer compositions.

9. Dry-up Liquid/Carrier Compositions

Liquids, active substrates and rubber chemicals are dried up on fineparticle carriers. The dry, free flowing powders are produced by addingthe powder to the liquid while mixing in a Hobart mixer until a dry,free-flowing powder is produced. From the weight of the liquid carriedon a carrier solids, one can calculate the carrying capacity of thecarrier powder.

The SAMS product from Example Two was compared with the control clay(Hydragloss 90) in terms of the carrying capacity of mineral oil andFlexon (Exxon) processing oil. These liquids were converted to dry,free-flowing powders with the carrying capacity expressed as the percentby weight of liquid (% active) present. The carrying capacity data isgiven in Table XII.

                  TABLE XII                                                       ______________________________________                                        CARRYING CAPACITY OF SAMS                                                     Carrier Powder     % Active                                                   ______________________________________                                        Liquid: Mineral Oil                                                           Control Clay       10                                                         SAMS from Example Two                                                                            58                                                         Liquid: Flexon Oil                                                            Control Clay       10                                                         SAMS from Example Two                                                                            60                                                         ______________________________________                                    

From data in Table XII, it can be readily seen that SAMS of the instantinvention has excellent carrying capacity when compared with the claycontrol. It is quite remarkable that clay has been converted into thefunctional carrier SAMS by the teachings of the instant invention.

10. Paint Coating Compositions

In order to provide protection and to produce a pleasing appearance, avariety of surfaces, such as wood, metal fabric, paper, or plastics, arecoated with clear flatting compositions containing dispersed orsuspended particles of a flatting agent which reduces the gloss or sheenof the coating and the coated substrate, preferably withoutsubstantially reducing the transparency of the flat coating. Forexample, wood finishes which serve to protect the surface againstabrasion and stain, yet do not conceal the beauty of the grain, are madeto simulate desirable hand-rubbed finishes by incorporating flattingagents therein which normally are dispersed fine particles of suchmaterials as silicas. The best effects are obtained with silicas ofuniform particle size down to the submicron range. Small size anduniformity are necessary to achieve a smooth coating without whitespecks or without a graying effect which would detract from theappearance of the coating.

For paint flatting application, 10 grams of SAMS from Example Two of theinstant invention was mixed with 350 grams of nitrocellulose lacquer(conforming to Military specification MIL-L-10287A-amendment 2, Type II,of issue 27, August 1959), and mixed for three minutes using the lowspeed setting of the Hamilton Beach #30 mixmaster. The lacquercontaining dispersed SAMS was tested for Hegman fineness of grind.

The lacqer containing dispersed SAMS from Example Two was evaluated forpaint flatting properties. A drawdown was made on Carrara glass using a#34 wire coatings application rod. The Carrara glass drawdowns wereallowed to dry for 45 minutes under dust-free conditions. Using theabove method, drawdowns were also made by using a control syntheticsilica normally used in this application.

Using the Gardner multi-angle gloss meter, the gloss and sheen values ofthe various drawdowns were measured at 60 degrees and 85 degrees,respectively. These values were compared with measured values obtainedwhen a control silica was dispersed in the lacquer.

SAMS of the present invention result in cleaner Hegman grinds andexhibit better clarity when dispersed in the lacquer.

Flatting data listed in Table XIII suggests that the novel SAMS of thepresent invention exhibit lower gloss and sheen values than the controlsilicas. Lower gloss and sheen values are preferred and advantageous forpaint flatting applications.

                  TABLE XIII                                                      ______________________________________                                        PAINT FLATTING EVALUATION                                                                      60 Degree 85 Degree                                          Flatting Agent   Gloss     Sheen                                              ______________________________________                                        SAMS (Example One)                                                                             10        21                                                 SAMS (Example Two)                                                                              8        16                                                 Control Silica   15        45                                                 (Zeothix 95)                                                                  ______________________________________                                    

A close examination of the data in Table XIII clearly shows the SAMScompositions of the instant invention as having superior flattingproperties compared with the synthetic silica control. It is quiteremarkable that clay has been converted into a value added functionalproduct by the teachings of the instant invention.

11. Detergent Compositions

Typical home laundry detergents are generally formulated as a 50-60%solids slurry and spray dried to give the familiar powdered products. Atypical home laundry detergent consists of the following ingredients:

    ______________________________________                                        Ingredient        Percent, by weight                                          ______________________________________                                        Sodium Tripolyphosphate                                                                         12-50                                                       Surface Active Agents                                                                           10-20                                                       Liquid Sodium Silicate                                                                          5-8                                                         Soil Redeposition Agents                                                                        0.5-1.5                                                     Fluorescent Dyes  0.05-1                                                      Water              2-12                                                       Sodium Sulfate    Balance                                                     ______________________________________                                    

Surface active agents mainly consist of anionic linear alkyl benzenesulfonate (LAS) and non-ionic alcohol based ethoxylates (AEO). Asurfactant is needed in the detergent to extend the functionalperformance of the detergent builder.

Non-ionic surfactants are added at a level of 4-6% (typical non-ionicsurfactants currently being used are Shell's Neodol 25-7 and 45-11)based on the weight of other ingredients of the detergent compositions.The resulting slurry is spray dried. Non-ionic surfactants contain smallfractions of short-chain molecules called "light ends." During the spraydrying step, the "light ends" do not incorporate into the finisheddetergent bead and go out of the dryer exhaust and result in a whitecloud referred to as "plume."

Detergent producers are anxious to cut down this "plume" and severalmechanical advances have been made to scrub the stack gases but thescrubbing process is not 100% effective. Also, the equipment required toclean the stack gases is very expensive.

We have found an inexpensive solution to the problem in which SAMS ofthe present invention can be used to convert the liquid non-ionicsurfactants to dry, free-flowing particulates so that dried-upsurfactant can be post added to the spray dried detergent formulation.Thus, SAMS compositions of the instant invention are useful fordrying-up non-ionic surfactants in the free-flowing form. Thus, SAMS canbe used in the detergent compositions to solve an air pollution problemcalled "pluming."

Neodol 25-9 surfactant (manufactured by Shell Chemical Company) wasdried-up on SAMS from Examples One and Two. The maximum amount of Neodolthat can be dried up is listed in Table XIV.

                  TABLE XIV                                                       ______________________________________                                        DRYING-UP NEODOL 25-9 ON SAMS PRODUCTS                                                         Flow Time % Active                                           Carrier          (seconds) Surfactant                                         ______________________________________                                        SAMS (Example One)                                                                             18        51.2                                               SAMS (Example Two)                                                                             15        55.9                                               Clay Control     86        10.0                                               ______________________________________                                    

From data in Table XIV above, it is clear that SAMS compositions ofExamples One and Two exhibit superior flow properties and dryingcapacity when compared with the corresponding control clay used inExample Two.

Thus, the method of drying up non-ionic surfactants results in superiorfree flowing surfactant powders. These surfactant powders can beefficiently used by post-adding to detergent compositions. Thus, SAMS ofthe instant invention are useful in detergent compositions and theseSAMS pigments impart superior properties which help in solving animportant air pollution problem.

12. Plastic Film Antiblock Compositions

Low density polyethylene (LDPE) and polypropylene (PP) film have atendency to stick together. This phenomenon is called "blocking." SAMSpigments of the instant invention were evaluated to determine if SAMScould be used as antiblocking agents in LDPE, PP and other plasticsfilms.

Approximately 1300 gram batches of LDPE and SAMS compositions fromExamples One and Two, as well as the control clay from Example Two, werecompounded in the 3# Banbury. Each sample was then granulated andextruded through the one and one-half inch Davis Standard Extruder usinga 20/100/60 mesh screen pack. Each sample extruded contained 90% LDPEGulf Resin 5200 and 10% of either the SAMS composition from Example Oneand Two, or the control clay from Example Two. Press-outs from eachconcentrate were made from each sample to determine the quality anddispersion of each material.

Film was then produced on the one-inch Killion extruder. All filmsamples were produced on the same machine on the same day at a constantrpm, identical temperature profile, and constant film thickness.

Film samples were heated after 24 hours of film aging to let theantiblock additive migrate to the surface of the film. The blockingforce, coefficient of friction (COF) and percent haze were determined oneach film sample. These results are summarized in Table XV.

                  TABLE XV                                                        ______________________________________                                        ANTIBLOCK COMPOSITION                                                         (FILM THICKNESS: 2 MILS)                                                                Antiblock   Blocking   COF,  %                                      Compound  Agent       Force, gm  g     Haze                                   ______________________________________                                        Gulf Resin 5200                                                                         None        76         0.6   11                                     Gulf Resin 5200                                                                         HG-90 Clay  74         0.5   12                                     Gulf Resin 5200                                                                         SAMS from   38         0.5   10                                               Example One                                                         Gulf Resin 5200                                                                         SAMS from   45         0.4    9                                               Example Two                                                         ______________________________________                                    

Data in Table XV clearly show that SAMS have better antiblockingproperties than the starting resin and the clay control. Also, the COFand the haze properties of the film containing SAMS are definitelysuperior to the film containing the clay control.

SYNTHESIS OF SAMS AS A FUNCTION OF B/C RATIO

Except as expressly noted below the procedures of Example One and Twowere followed using laboratory reactors of two-liter, one-gallon ortwo-gallon capacity in carrying out the examples below which areotherwise abbreviated to focus on the variables changed. Experimentationwas performed on a laboratory scale.

EXAMPLE THREE

A reaction in accordance with Example Two was carried out at 135 psi,for one hour of reaction time using Hydragloss 90 and a 2.5 mole ratiosodium silicate to illustrate the novelty of the invention over a widerange base to clay ratios. Conditions and results are shown below inTable XVI.

                  TABLE XVI                                                       ______________________________________                                        SAMS SYNTHESIS AS A FUNCTION OF B/C RATIO                                                            Monovalent                                             Base to      Oil       Cation Exchange                                        Clay Ratio   Absorption,                                                                             Capacity,                                              B/C          ml/100 g  meq/100 g                                              ______________________________________                                        Clay Control  30        2                                                     .20           89        72                                                    .35          127       123                                                    .50          164       170                                                    .70          124       189                                                    .90          122       186                                                    ______________________________________                                    

This clearly points to the fact that a wide variety of SAMS compositionsof high oil absorption and high ion exchange capacity, when comparedwith control clay, can be prepared by the teachings of the presentinvention.

EXAMPLE FOUR

To illustrate the present invention in regard to the use of differentalkali metal silicates, a reaction of potassium silicate (Kasil No. 1)and Hydragloss 90 at 120 psi for one hour at 10% solids yields theresults set forth in Table XI.

                  TABLE XVII                                                      ______________________________________                                        SAMS SYNTHESIS FROM POTASSIUM SILICATE                                        Base to       Oil        Surface                                              Clay Ratio    Absorption,                                                                              Area,    Brightness                                  B/C           ml/100 g   m.sup.2 /g                                                                             %                                           ______________________________________                                        Hydragloss 90 (Control)                                                                     43         22       91                                          0.25          88         27       87.0                                        0.50          89         19       88.1                                        0.75          142        22       91.1                                        ______________________________________                                    

Data in Table XVII clearly shows that the alkali metal potassium canalso be used in the synthesis of unique SAMS compositions.

EXAMPLE FIVE

In accordance with the teachings of this invention, Example Five showsthe formation of SAMS compositions at B/C ratios of 1.0 to 2.0, usingalkali metal silicate bases of different SiO₂ /Na₂ O molar ratios. Toexemplify this aspect of the invention, a Hydragloss 90 clay was reactedwith 2.5 and 3.3 mole ratio sodium silicate at approximately 100 psi forone hour at 10% solids. The results are set forth in Table XVIII.

                  TABLE XVIII                                                     ______________________________________                                        SYNTHESIS OF SAMS                                                             AT HIGH B/C BATCH COMPOSITIONS                                                     Base to                 Sur-  Cation                                          Clay    Oil             face  Exchange                                                                              Bright-                            Test Ratio   Absorption,                                                                             Struc-                                                                              Area, Capacity,                                                                             ness                               No.  (B/C)   ml/100 g  ture  m/g   meg/100 g                                                                             %                                  ______________________________________                                        Hydragloss                                                                              30       VLS     20    2-3     91.0                                 90 Control                                                                    1*   1       162       MS    24    141     91.7                               2*   2       193       HS    19    191     93.0                               3**  1       187       HS    16    159     92.6                               4**  2       115       LS    11    136     91.2                               ______________________________________                                         *2.5 Silicate Mole Ratio (SiO.sub.2 /Na.sub.2 O)                              **3.3 Silicate Mole Ratio (SiO.sub.2 /Na.sub.2 O)                        

Data in Table XVIII clearly show the formation of SAMS compositions atB/C ratios equal to and greater than 1.0 using alkali metal silicatebases of different SiO₂ /Na₂ O molar ratios. The SAMS compositions hadoil absorption values which would correspond to materials having fromlow (LS) to high (HS) structure. TEM FIGS. 22 and 23 also show the sameunique SAMS composition and morphology of SAMS compositions prepared atB/C ratios of 0.5 and 0.75 (FIGS. 18 through 21).

FIG. 5 shows a comparison of the FT-IR spectra of Hydragloss 90 controlclay, SAMS from Example Two prepared at a B/C of 0.5, and SAMS fromExample Five prepared at a B/C of 1.0 and 2.0. A sodium silicate havingan SiO₂ /Na₂ O mole ratio of 2.5 was used in the SAMS synthesis. Theonly difference observed in the IR spectra of the SAMS compositionsoccurred in the 1200-950 wavenumber region in the Si-O stretching peak.As the B/C of the SAMS composition increased the peak became broader andless detailed. This would indicate an increase in the amount ofamorphous material present in the SAMS compositions. The TEMS's andFT-IR spectra clearly show that the unique SAMS compositions can beformed at B/C ratios of one and greater.

To further demonstrate the functionality feature of the variety of SAMScompositions prepared at different B/C ratios, the products from Tests 1through 4 were evaluated as functional extenders in a typical paintformulation similar to that described earlier. In Table XIX the productsfrom Tests 1 through 4 were compared in contrast ratio with Zeolex 80,Hydragloss 90 and Satintone 5, a commercial, high brightness calcinedclay.

                  TABLE XIX                                                       ______________________________________                                        PAINT PROPERTIES OF SAMS                                                      VERSUS B/C OF BATCH COMPOSITION                                                                 Silicate           Contrast                                 Test No.  B/C     Mole Ratio Structure                                                                             Ratio                                    ______________________________________                                        1         1       2.5        MS      .977                                     2         2       2.5        HS      .978                                     3         1       3.3        HS      .975                                     4         2       3.3        LS      .970                                     Satintone 5       --         VLS     .975                                     Hydragloss 90     --         VLS     .976                                     Zeolex 80         --         LS      .973                                     ______________________________________                                    

As noted in Table XIX, the SAMS composition having medium to highstructure produced excellent contrast ratio values which equalled orsurpassed values for commercially available calcined clays or silicas inpaint properties.

EXAMPLE SIX

To illustrate the present invention in regard to the use of silicatescomprised of various SiO₂ /Na₂ O ratios, a reaction of Omnifil andvarious silicates at a pressure of 120 psi for one hour of reaction timeat 10% solids yields the results set forth in Table XX.

                                      TABLE XX                                    __________________________________________________________________________    SYNTHESIS OF SAMS AS A FUNCTION OF SILICATE MOLE RATIO                               Silicate  Monovalent                                                      Base to                                                                           Mole      Cation Sur-                                                     Clay                                                                              Ratio                                                                             Oil   Exchange                                                                             face                                                                              Bright-                                           Test                                                                             Ratio                                                                             (SiO.sub.2 /                                                                      Absorption,                                                                         Capacity,                                                                            Area,                                                                             ness, Struc-                                      No.                                                                              (B/C)                                                                             Na.sub.2 O)                                                                       ml/100 g                                                                            meq/100 g                                                                            m.sup.2 /g                                                                        %     ture                                        __________________________________________________________________________    1  .50 3.33                                                                              161   115    24  83.5  MS                                          2  .75 3.33                                                                              167   149    20  85.8  MS                                          3  .50 2.50                                                                              156   143    25  85.5  MS                                          4  .75 2.50                                                                              148   175    21  85.9  MS                                          5  .50 1.00                                                                              123   148    28  84.0  LS                                           6*                                                                              .75 1.00                                                                               83   216    28  85.1  LS                                          Omnifil                                                                              --   37   2-3    20  82.0  VLS                                         (Control)                                                                     __________________________________________________________________________     *XRD pattern showed presence of zeolitic material                        

As can be seen from the data in Table XX, SAMS compositions having lowto medium structure were formed under the preferred conditions of B/Cless than 1.0 using alkali metal silicate bases of varying SiO₂ /Na₂ Omolar ratios. Low structured SAMS compositions prepared in Tests No. 5and 6 using sodium metasilicate. The XRD pattern of Test 6 showed thepresence of a zeolitic material. FIG. 6 shows a comparison of theinfrared spectra of the SAMS compositions of Example Six prepared at aB/C ratio of 0.5 using the different molar ratio sodium silicates. TheIR spectra of the SAMS prepared from the 2.5 and 3.3 mole ratio silicateare essentially identical and closely resemble the IR pattern of theSAMS compositions of Example One, Two and Five (FIGS. 3, 4 and 5). TheIR spectrum of the SAMS prepared with meta silicate more closelyresembles that of the starting clay (FIG. 3), reflecting the lowersilicate content of the starting reaction mixture. This is especiallytrue in the 1200-950 wavenumber Si-O stretching region. It must beconcluded, based on the physical and analytical data, that unique SAMScompositions similar to those produced in Example One and Two wereformed by reacting clay with sodium silicates of SiO₂ /Na₂ O molarratios of 1.0 to 3.3 at B/C ratios less than 1.0.

EXAMPLE SEVEN

To illustrate the effectiveness of the present invention on a claypigment produced from another locale, a delaminated Central Georgia clay(Hydraprint) having the properties shown in Table XXI was employed for athree-hour reaction time at 120 psi and 10% solids, using a 3.33 moleratio sodium silicate. Results of the reactions are shown in Table XXI.

                  TABLE XXI                                                       ______________________________________                                        SYNTHESIS OF SAMS                                                             FROM CENTRAL GEORGIA CLAY                                                     Base to    Oil          Surface                                               Clay Ratio Absorption   Area,                                                 (B/C)      ml/100 g     m.sup.2 /g                                                                             Structure                                    ______________________________________                                        Hydraprint  49          13       VLS                                          (Control)                                                                     0.25       153          19       MS                                           0.50       179          14       HS                                           0.75       171          14       MS                                           ______________________________________                                    

The oil absorption data shown in Table XXI would suggest that uniqueSAMS compositions of medium to high structure can be produced by thereaction of a relatively coarse particle size, low surface area claysuch as Hydraprint with an alkali metal silicate base.

EXAMPLE EIGHT

To illustrate the importance of controlling reaction time andpressure/temperature in the SAMS synthesis, a series of SAMS reactionswas conducted in which pressure and reaction time were varied between100-150 psi and one to three hours, respectively. Results of the testsare shown in Table XXII. The reactions were conducted at 10% solidsusing a Hydraprint, middle Georgia delaminated clay, and a B/C ratio of0.8. A 3.3 mole ratio sodium silicate was used in the tests.

                  TABLE XXII                                                      ______________________________________                                        SYNTHESIS OF SAMS AS A FUNCTION OF                                            REACTION, PRESSURE AND TIME                                                                   Bright- Oil                                                   Pressure,*                                                                            Time,   ness,   Absorption       SA,                                  psi     hrs     %       ml/100 g                                                                              XRD      m.sup.2 /g                           ______________________________________                                        100     1       89.2    134     SAMS     13                                           2       90.0    135     SAMS     11                                           3       90.3    145     SAMS     11                                   120     1       89.9    131     SAMS     11                                           2       90.6    133     SAMS     11                                           3       91.1    157     SAMS +   112                                                                  Trace Z**                                     135     1       90.3    137     SAMS      9                                           2       91.2    156     SAMS +   33                                                                   Trace Z                                               3       91.3    161     SAMS + Z 91                                   150     1       90.6    144     SAMS     10                                           2       91.5    158     SAMS +   49                                                                   Trace Z                                               3       91.5    150     SAMS + Z 124                                  Hydraprint      87.5     42              14                                   (Control)                                                                     ______________________________________                                         *Corresponding temperatures can be found in steam table                       **Zeolite                                                                

The above tests illustrate the wide variety of SAMS compositions thatcan be produced by reacting clay and alkali metal silicate. Brightness,oil absorption and surface area of the resulting SAMS compositions canbe changed by varying reaction time and steam pressure (temperature).The data show that if the presence of zeolitic material in the SAMScomposition is undesirable, it can be eliminated by reducing reactionpressure and/or time.

EXAMPLE NINE

To illustrate the uniqueness of the clay-sodium silicate reaction, testswere conducted in which Hydragloss 90 east Georgia clay was reacted withboth a 2.5 molar sodium silicate and sodium hydroxide at B/C ratios of0.75 to 5.0. The reactions were conducted at 10% solids at 120 psi fortwo hours. Results of the tests are given in Table XXIII.

                  TABLE XXIII                                                     ______________________________________                                        COMPARISON OF SODIUM SILICATE                                                 WITH SODIUM HYDROXIDE AS BASE IN                                              THE SAMS SYNTHESIS                                                            Base to                                                                       Clay                                                                          Ratio,        Brightness,                                                                             OA,    SA,                                            (B/C) Base    %         ml/100 g                                                                             m.sup.2 /g                                                                         XRD                                       ______________________________________                                        0.75  Silicate                                                                              92.1      147    90   SAMS                                      1     Sllicate                                                                              90.9      102    228  SAMS +                                                                        trace Zeolite                             3     Silicate                                                                              92.0      90     246  Trace SAMS +                                                                  Zeolite                                   5     Silicate                                                                              93.5      104    7    Amorphous                                 0.75  NaOH    81.0      82     20   Hydroxy sodalite*                         1     NaOH    74.6      78     15   Hydroxy sodalite*                         3     NaOH    83.5      64     17   Hydroxy sodalite                          5     NaOH    81.5      60     21   Hydroxy sodalite                          Hydragloss 90                                                                           91.0      43       22.0                                             ______________________________________                                         *XRD also showed presence of kaolinite.                                  

The reaction with sodium hydroxide formed only hydroxy sodalite. Inaddition, the low brightness, oil absorption and surface area valuesalso show that no SAMS compositions were formed. In contrast, the sodiumsilicate reaction produced SAMS compositions having increasedbrightness, structure (oil absorption) and surface area. The XRDanalysis of the silicate reaction products showed the presence ofzeolites at B/C ratios of 1.0 and higher. The amorphous character andlow surface area of the B/C=5 silicate reaction indicated the formationof a new phase.

FIG. 7 compares the spectra of the silicate reaction products in TableXXIII. The spectra show the presence of SAMS but also show the increasein zeolite formation at the higher B/C ratios as the Si-O stretchingpeak (1200-950 wavenumber) becomes sharper and the peaks typical ofkaolin located between 800 and 400 wavenumbers disappear.

FIG. 8, likewise, compares the IR spectra of the sodium hydroxidereaction products. The Si-O stretching peak (1200-950 wavenumbers) issharper, indicating the formation of a crystalline phase (hydroxysodalite), and the loss of peaks in the 800-400 wavenumber region isobserved at lower B/C ratios than for the silicate reaction.

SUMMARY

As suggested by the above examples, the materials of the presentinvention may be used as effective pigment (titanium dioxide) extendersin paint and paper applications, as functional fillers or reinforcingagents in plastics and elastomers, as a catalyst support and carrier incatalyst preparation, as a thixotrope, as a conditioning and free flowagent, and in defoamer compositions. Because of their low abrasioncharacteristics, the materials of the present invention may be used tofill Xerox and electrostatic copier papers. Products of the presentinvention can also be used in a variety of specialty applications and asan opacifier, a diazo paper filler, a flatting agent, in siliconerubbers and other applications.

In addition, the SAMS compositions, because of their unique physical andchemical properties, may be used in certain catalytic applications ifthey are first exchanged with hydrogen, ammonium or other suitablecation; i.e., either as a separate particle or intimately mixed with thecomponents of a hydrocarbon conversion catalyst. Moreover, the widevariation one can achieve in surface area, pore volume, SiO₂ /Al₂ O₃ratio, and ion exchange capacity (solution or gas phase) suggest theirapplication for emission control catalysts and in metal scavenging, andin the clean-up of residue materials and/or resid-type feeds to fluidcatalytic cracking units in particular.

In the preferred embodiment of the invention, x is an integer of 0.01 to2.0, y is an integer of at least 2.0 and preferably 2.0 to 20.0 and z isan integer of 1.0 to 5.0.

The terms Hydraprint, Hydragloss, Huber 90C, Omnifil, Hydrasperse,Hycal, Zeolex 23, Hydrex, Zeolex, Zeolex 23P, Zeo, Zeosyl, Zeofree andZeodent used herein are trademarks of the J. M. Huber Corporation.Hi-Sil is a registered trademark of PPG and Ansilex is a registeredtrademark of Engelhard Corporation.

Although a specific preferred embodiment of the present invention hasbeen described in the detailed description above, the description is notintended to limit the invention to the particular forms or embodimentsdisclosed herein. The present disclosure is to be recognized asillustrative rather than restrictive. It will further be obvious tothose skilled in the art that the invention is not so limited. Theinvention is declared to cover all changes and modifications of thespecific examples of the invention herein disclosed for purposes ofillustrations, which do not constitute departures from the spirit andscope of the invention.

What is claimed is:
 1. A paint composition which contains an alkalimetal alumino-silicate having a composition in terms of mole ratio ofoxides as follows:

    xM.sub.2 O:Al.sub.2 0.sub.3 :YSiO.sub.2 :zH.sub.2 O

where x is the number of moles of alkali metal oxide, M is an alkalimetal, y is the number of moles of SiO₂ associated with the alkali metalaluminosilicate compositions, and z is the number of moles of boundwater, and having the morphology of rimmed particles as depicted in anyone of TEM FIGS. 18-23.
 2. A paint composition which contains anessentially x-ray amorphous alkali metal alumino-silicate having acomposition in terms of mole ratio of oxides as follows:

    xM.sub.2 O:Al.sub.2 O.sub.3 :YSiO.sub.2 :zH.sub.2 O

where M is the alkali metal, x is the number of moles of alkali metaloxide and is between 0.01 to 2.0, y is the number of moles of SiO₂ inthe alkali metal aluminosilicate composition and is greater than 2.0,and z is the number of moles of bound water and is 1.0 to 5.0, saidalkali metal alumino-silicate having attenuated kaolin peaks in the XRDpatterns from the kaolin remnants in the compositions and having thecharacteristic IR scan labelled SAMS shown in any one of FIGS. 3-6 andwhich are shown by any one of TEM FIGS. 18-23 to be altered kaolinplatelets integrated with a rimmed area of essentially amorphous alkalimetal silicate base-kaolin clay reaction product.
 3. A paint compositionaccording to claim 2 wherein the alkali metal silicate is sodium and hasa composition in terms of mole ratio of oxides, as follows:

    xNa.sub.2 O:Al.sub.2 O.sub.3 :YSiO.sub.2 :zH.sub.2 O

where x is the number of moles of sodium oxide and is between 0.01 to2.0, y is the number of moles of SiO₂ in the alkali metalaluminosilicate composition and is greater than 2.0, and z is the numberof moles of bound water and is 1.0 to 5.0.
 4. A paint compositionaccording to claim 1 wherein the alkali metal aluminosilicatecompositions have an oil absorption range of at least about 40 ml/100 gand a surface area range of about 2 to 300 m² /g.
 5. A paint compositionaccording to claim 2 wherein the alkali metal aluminosilicatecompositions have an oil absorption range of at least about 40 ml/100 gand a surface area range of about 2 to 300 m² /g.
 6. A paint compositionaccording to claim 3 wherein the sodium metal aluminosilicatecompositions have an oil absorption range of at least about 40 ml/100 gand a surface area range of about 2 to 300 m² /g.
 7. A paint compositionaccording to claim 1 wherein the paint is a latex.
 8. A paintcomposition according to claim 2 wherein the paint is a latex.
 9. Apaint composition according to claim 1 wherein the alkali metalaluminosilicate is present in sufficient amounts to function as apigment opacifier.
 10. A paint composition according to claim 2 whereinthe alkali metal aluminosilicate is present in sufficient amounts tofunction as a pigment opacifier.
 11. A paint composition according toclaim 1 wherein the alkali metal aluminosilicate is present insufficient amounts to function as a flatting pigment.
 12. A paintcomposition according to claim 2 wherein the alkali metalaluminosilicate is present in sufficient amounts to function as aflatting pigment.